Self-Awareness Achieved Through The Struggles In and Out of Society

The main characters revolving around each of these pieces of literature, The Adventures of Huckleberry Finn by Mark Twain, Emma by Jane Austen, and My Name is Asher Lev by Chaim Potok, have been positioned in different facets of society.Each of the protagonists have been endowed with qualities, traits and profiles that can strike attention for a reader, for an easier follow-through on each character’s progression or development as a character, at the same time the novel nears it climax and end.Huck, Emma and Asher have detached themselves from their old principles and life perspectives, as described by a number of literary techniques, and have entered into a new phase of self-realization, consciousness, awareness – the becoming of a new person.Huckleberry Finn, among the three protagonists, is considered to have been immersed in the most unlucky circumstances. Coming from the bottom sector of the society, Huck, as a child had formed a grave loathing for the society. He should undergo an enduring series of obstacles before he becomes the final and developed character in the story. Along the progression of the novel, Huck has turned this loathing into a substantial amount of doubt and distrust, but, we continually see Huck repeatedly rejected and violated by society. It was as if society turned him down when he desperately needed it.Consequently, Huck conjures up his independence from this society. Coming from this point, we can extrapolate Huck’s development as a character. There would only be two ways in Huck’s face, either he becomes a part of the society he despises or totally cut himself away from it.Emma Woodhouse, the female protagonist of Jane Austen, is a brilliant woman with all the money and approval of everyone around her. But, as the story progresses, we may realize that Emma could have had much of what she should actually have.Taken from the novel, Emma might have been to controlling of circumstances – things going her own way, and must have viewed a little too good of herself. This takes us to Austen’s clues on Emma’s flaws that shall play a great deal on the future blossoming of events and conflict, as well as, Emma’s development as a character. This is important as one reads through the progression of the novel and Emma.Asher Lev is the most distinct character of the three having rooted from a very restricted Jewish group. In his early years, Asher has developed an inclination towards the arts and eventually developed a talent for it.Restricted his community is – religious, for that matter, Asher is obliged to submit himself to the strict rituals of being a Hasidic Jew. An internal conflict within Asher begins to boil as he must choose between art and religion. Questions, such as, obligation and passion, emotion and priority will be raised in the entire novel. And the same questions shall guide the reader into Asher Lev’s character development and the rev elation of the novel itself.The Adventures of Huckleberry Finn is set before the eradication of slavery which was of very controversial value. And this setting has become the major stir in Huck’s character development. Huck Finn is a non-conformist. He doesn’t readily accept the conventions of society. In this novel, slavery as a major subject, Huck was faced with decisions that heavily moral in nature. These decisions, which were controversial enough, left a very significant change in Huck Finn’s emotional and moral development. This is evident as he helps a slave, Jim, to find his way to freedom.Huck Finn may have had a difficult time overcoming societal pressures on his non-conformism but this is Mark Twain’s way of characterizing Huck as a person who is independent of society – which is the very point of his development as a character. Huckleberry Finn developed as a character because of his own doing. He developed as an individual by drawing h is own conclusions of the world apart from himself. His choice, his non-conformism, diverged into many factors that molded his final self in the novel.Emma, on the other hand, extracts her character development from the conflicts within the society. This is her distinction from Huck Finn. She hails from an affluent sector of the society and has been chained in its very strong limitations – confined in what is acceptable at the time. Her matchmaking practice has caused her the very same conflicts that shall allow her development as a character in the novel.These conflicts, apart from development, showed Emma a better picture of how her actions created an inflicting effect on the people in her society. This is the root of Emma’s self-realization.

Discuss the theme of the Dream in the book Of Mice and Men Essay

None of the people on the ranch have freedom, and freedom was what George and Lennie wanted. Crooks, Candy and Lennie are victims, Crooks because of his back, where a horse had kicked him, Candy because of his hand, which he lost on the ranch, although he got two hundred and fifty bucks in compensation and Lennie is a victim because of his lack of knowledge. The main dream in the book â€Å"Of Mice and Men† is George and Lennie’s dream. Their dream is to have their own land where they will grow whatever they like, and to have a variety of animals, and Lennie will get to look after the rabbits, if he behaves well. The rabbits are all he talks and thinks about – the perfect land and the rabbits that he will look after if he behaves himself. â€Å"Don’t you think of nothing but rabbits?† The land will be ten acres, have a windmill, a little shack and chicken run. It will have a kitchen and plenty of food and water. They will build a smoke house where they will smoke the bacon, the ham, and the sausages. They’ll kill a pig or rabbit each Sunday. They’ll can fruits. They’ll also sell eggs and milk. They want to be answerable to nobody, to have freedom and be independent. Also, like Lennie says with a lot of enthusiasm, â€Å"An` live off the fatta the lan`† This is a dream that George believes will not come true, (but he continues as though the dream will come true to lure Lennie to behave himself.) because they don’t have the money and Lennie is always getting in some sort of trouble and then, they have to run away. He doesn’t mean to do any harm. â€Å"All the time he done bad things but he never done one of ’em mean† Soon Candy gets to know about their dream, and this is the only part of the book where it seems that the dream is only around the corner. With Candy’s three hundred and fifty bucks and George’s and Lennie’s fifty bucks each coming at the end of the month, which makes a total of four hundred and fifty bucks, George says he could swing the owners for that as the lady needs an operation. George has a dream of his own which is a life without Lennie. If he didn’t have Lennie with him all the time, â€Å"When I think of the swell time I could have without you, I go nuts. I never get no peace.† If he also didn’t have Lennie ‘on his tail’ all the time, he could maybe even have a girl. This dream does come true at the end, but George had to kill Lennie or otherwise Curley would have come and killed Lennie himself. George learnt from Candy’s mistake of letting someone else kill his dog, so he killed Lennie himself making sure that the gunshot would not give Lennie any pain. Lennie’s life is ended, also with the dream as Lennie and George are talking about the dream – until Lennie is killed like an animal. Candy’s dream was to be happy. The only time he was really happy was when he was a child. Candy has no other relatives, so he thought he’d be happy living with George and Lennie. Candy is heartbroken when he finds out that Lennie has killed Curley’s wife. Candy knows that their dream cannot come true now, because Lennie was part of the dream and now he is dead. Also, when Candy’s dog was shot, Candy covered his eyes with his arm. â€Å"Old Candy lay down in the hay and covered his eyes with his arm.† And this was what he did when his dream was shattered. We do not know what happened to Candy or George after Lennie was killed, as the story ended there, so the death of Curley’s wife ended two dreams, but the death of Lennie made George’s second dream come true. Even though he didn’t like killing Lennie, he didn’t want to let someone else kill him. I suppose George thought it was the last straw – if he is killing unknowingly, he could kill again. They could not keep running from everything he did wrong. He would get caught one day, and be killed. Curley’s dream was to be big like Lennie and this is why Curley picked a fight with Lennie and he lost. He didn’t give Lennie a chance to show him that he was not against him, but straight away headed for Lennie and started asking him questions. George had told him not to speak, so he didn’t answer. Curley really got angry. George answered for him and he answered, ‘An’ you won’t let the big guy talk, is that it?’ He wants to be big and tall. He picks fights with anybody that is larger, in a way superior to him. He only has respect for Slim; we know this because he listened to Slim. â€Å"I think you got your han’ caught in a machine.† He knows what really happened. He didn’t want to get laughed at either, so he listened and obeyed Slim’s instruction. â€Å"But you jus’ tell an’ try to get this guy canned and we’ll tell ever’ body, an’ then will you get the laugh.† Curley agreed to this statement, otherwise he will be laughed at for starting the fight and then losing it. Even though Curley’s hand was totally ruined, and Lennie got a couple of bruises and cuts nobody got in any more trouble. When his wife was killed he was really mad. Not mad for losing a loved one. He was mad at Lennie for killing her, and instead of staying with his wife, he hurried off to find Lennie and to kill him. We notice that although Curley was very protective over his wife, he didn’t show any interest in her, and showed no signs of love. Nobody liked Curley, not even his wife. Curley’s wife was an outcast, because she is the only female on the ranch and wore a lot of red. We can sense she is heading for trouble, because of the way she flirted with all the men on the ranch. Red lipstick and red finger nails shows a sign of danger. Curley’s wife’s dream was to become a movie star, and have nice clothes. This dream only came about because; some guy had said that she was a natural. â€Å"this guy says I was a natural† Her dream was shattered because she didn’t receive a letter, this guy had promised to send to her. According to her, she thought her mother had thrown it away. We get the feeling that he didn’t actually send the letter. She really thought that her mother had thrown it away and only for revenge, she got married to Curley. She didn’t love Curley, nor even liked him. She’s not interested in Curley and Curley has no interest in her, but she is always looking for him, as an excuse, to talk to other guys. The other guys think she’s a tart, and is ‘jail bait’. Crooks has a dream, which is when he was a little child he remembered he had two brothers and they used to do everything together. His dream is to be back with his family. â€Å"I remember when I was a little kid on my old man’s chicken ranch.† He became negatively cynical. He doesn’t believe life will get any better and he thinks that people always behave selfishly or dishonestly. Crooks is lonely and the only one who has respect for him is Slim. When he was small he used to play with people that weren’t black and this would upset his father. He didn’t understand why until he was older. People called him a nigger and he is the only black person on the ranch. When he was a child, his family was the only black family for miles. Crooks had no other dreams; he just wanted friends that won’t criticize him, because of his colour. None of the dreams came true, and are all crushed and shattered, because George’s dream didn’t mean that he didn’t want Lennie at all, he wanted him, but not all the time. Lennie had to be killed and that ends another two dreams. Candy’s dream was to be a part of George and Lennie’s dream, but as Lennie was killed, his dream also vanished. Curley’s dream was to be big and as he’s a grown man he won’t grow any more. Crook’s dream is to be back with his family, but it is impossible to go back in time. Curley’s wife is dead which ends another dream. We see that John Steinbeck didn’t make anybody’s dream come true. Anjana Patel English coursework 2nd January 2001

Plato’s Allegory of the Cave and Advertisements

Julian Figueroa (#30973127) 1 An Allegory of Advertisements How does Plato’s allegory influence the way we consume art today? Every minute of every day, millions of people are exposed to advertisements. They plague televisions, streets, radio waves, and all means of communication. These advertisements employ many methods of persuasion and their influence is irresistible. Just like prisoners in Plato’s Allegory of the Cave, we are told every day to invest our time and interest into the subject of these advertisements, and to accept the forms of reality they serve us.Whether it be a commercial for a must-have new car, to a spot featuring desirable fast food, or to magazines with photoshopped models; we are seduced to accept these false forms of reality. In actuality, the car is hardly distinguishable from models in the years past, the food is not near as glossy and fresh as the commercial depicts, and the bodies of models have unfeasible proportions. Like the prisoners in the cave, we still accept these forms to be reality, even though they are imitations and falsities of their actual subjects.Puppeteers, like prisoners, are still within the boundaries of the cave, and some believe in their imitations whilst others know the falsehood they are presenting; just like advertisers of today. Even philosopher-kings must be part of the cave in certain ways, as they contribute their own forms of imitation to the prisoners, akin to puppeteers. The Allegory of the Cave has an abundance of meaning to our generation and future generations to come, as the themes and elements it contains relate directly to our society’s consumption and production of promotional media.In Plato’s allegory, several metaphors are summoned to illustrate the effect of education on the soul. The allegory starts with the description of a cave; a place containing prisoners, shadows, puppeteers and fire. The prisoners are bound to look at the shadows, cast upon the wall by the fire and the objects utilized by the puppeteers. There is an exit to the cave, which is illuminated by the light from the sun outside. The outside represents true knowledge whereas the inside of the cave represents ignorance; a reality other than the truth.Plato considers the puppeteers to essentially be artists; using their creations to depict a false reality for the Julian Figueroa (#30973127) 2 prisoners. However, those who free themselves from the cave are the only ones who can realize true form. Those who do this are labeled as the philosophers. For the purposes of this essay, only the aspects of art and art interpretation in the allegory are important. What makes the allegory decisive in comparing it to our consumer-producer society is that the metaphors Plato uses directly correlate to the mantras of advertising.Notwithstanding, for any of this argument to be relatable to Plato’s allegory, which primarily focuses on artists and their creations, one must first know wha t makes promotional media a form of artistic expression. Let us assume Plato’s definition; that art is a poor imitation of reality. He views the creators of art, or as he sees them, imitators â€Å"by nature third from the king and the truth† (Republic, 597e). Artists in publicity take this notion and exaggerate it to the furthest degree. For instance, what makes us want a Burger King burger over any other local burger joint product?The answer to that is clear; advertising. Without its advertising in mass, one wouldn’t be able to distinguish a Burger King product over any other competitor’s. On the contrary, we are drawn towards their burgers because of their glorious depictions in media. From passing the giant billboards of lucious burgers, to seeing a family enjoy them on a television commercial; we are told to believe that these titillating combinations of veggies and protein are absolutely marvelous. These advertisements are nothing but mere deception s of reality.The billboards show us enlarged, crisp patties and fresh vegetables, when in reality, there is no guarantee of such a thing. Therefore they are what Plato defines as art; imitations of reality. Another example would be political commercials, which skew the truth in a variety of ways. From showing an out of context quote from their opponents, to showing themselves speak to a crowd with uplifting music in the background, politicians use the art of media to manipulate the public from seeing the truth. Advertising is a very sharp form of communication from puppeteer to prisoner; and it directly relates to Plato’s allegory.Most of us accept these false forms of reality regardless. Millions of people watch misleading commercials for a product, but they still purchase it in the end. Millions of people knowingly vote for politicians who offer false promises and deceptions, but they still return to vote for the same people in future elections. Like the repetitious cycle o f puppeteers feeding prisoners art in the allegory, Julian Figueroa (#30973127) 3 consumers of today lust for producers to fill their fair supply as well. So how do we exit this cycle? Through education and enlightenment.Plato believes that any ruler of men must pursue in â€Å"calculation, geometry, and all the preliminary education required for dialectic† (536d). He also believes that â€Å"no free person should learn anything like a slave. † (536e). Therefore, one must exercise in their own free will to truly become educated. Plato believes that to be truly educated, one must question and study the fundamental nature of knowledge, reality, and existence. By doing this, along with decades of physical training, mathematical science, dialectic training, and political discovery, one then becomes a philosopher-king; the third human element in the allegory of the Cave.However, unlike the puppeteers and the prisoners, the philosopher-kings reside outside the cave, and they harness the ability to see true forms, not mere shadows. So if we live in a society of art production and art consumption, who are the modern day philosopher-kings? There is no simple answer to that question, and this is where Plato’s allegory begins to cave in on itself (pun intended). Plato is a philosopher himself, and by channelling his ideas through Socrates in The Republic, he creates a forum. Socrates starts the allegory of the Cave with the word â€Å"imagine† (514a).The definition of the term â€Å"imagine† is to believe something unreal or untrue to exist. Therefore, Socrates is envisioning an imitation of reality with his allegory, making him an artist. Based on his definitions, Socrates (and therefore Plato) dips his feet back into the cave. If all philosophers followed the same methods of Plato, in terms of creating art forms of philosophy, doesn’t that mean that we are all either puppeteers and/or prisoners? If, in conclusion, philosophers subject their knowledge in an understandable format to puppeteers and prisoners, they are essentially creating art; which means nobody is truly free from the cave.Yet, to generalize philosophers exactly as puppeteers would also be incorrect, contrary to the Allegory. As discussed previously, philosophers only dabble in the art of imitation. This does not make them true puppeteers. Whereas philosophers are able to educate without false forms of reality, true puppeteers are only showing imitation. So what forms do puppeteers accept to be true? Imitation or reality? Relating back to the â€Å"Burger King Theory†, do the Julian Figueroa (#30973127) 4 puppeteers knowingly accept their imitations?Most likely not, as they are aware of the flaws in their advertisement. If a Burger King representative accepted their imitations as reality, they would probably be tempted to eat burgers everyday and eventually die from malnutrition or diabetes. Rather, these representatives are still tru e puppeteers and are therefore still in the dark among the prisoners. So what reality is accepted from the puppeteers? If we look at the representatives of, say Ford, for example’s sake, we find that they reject their own imitations of reality, or art, but that they still consume in similar ways to prisoners.A representative of Ford may make the commercials for the newest model of truck, but does that dictate that they necessarily drive one? Not at all. At the same time, it is not an impossibility either, and their experience as an advertiser, or artist, may even lead them into believing that it is necessary to buy the newest model every year. After all, they are surrounded with their advertisements constantly, influencing them even more so than a consumer, so couldn’t they eventually accept them to be correct?Unless one becomes a monk and sanctions themselves completely away from society, which Plato would most likely condemn, one will always be a target of advertisem ents. Therefore puppeteers must be partially prisoners in that regard, as they will fall target to other puppeteer’s or even their own shadow imagery. This concept works symbiotically with the notion that philosophers are partially puppeteers; as Plato concedes to enjoying the influence of children’s tales on youth, stating that mothers â€Å"will shape their children’s souls with stories much more than they shape their bodies by handling them. † (377c).He openly admits to enjoying some forms of art, and accepting them even if they â€Å"are false, on the whole, though they have some truth to them. † (377a). Hence, he is also as prisoner in that regard, akin to a puppeteer. This draws yet another parallel to art consumption in our modern day society; even a philosopher in our day and age must appreciate certain things to survive, and may be drawn towards imitation of reality through advertisement; car commercials, food spots, or anything. With the acceptance of this concept, the consequence is that everyone in our modern society still resides at least somewhat within the boundaries of the Cave.Is this not true? Can anyone truly claim in this era that they are free from advertisements? Julian Figueroa (#30973127) 5 Can we go one day without seeing a commercial and not remotely showing interest, even in our subconscious? In some countries around the world, it is not even an option to reject an imitation of reality. For example, citizens of Australia are forced by law to vote, and in that sense, it is impossible not to be persuaded by inevitably deceptive political advertisements. The relation of things such as politics, billboards for burgers, and car commercials to the allegory of the Cave is certainly an odd concept to comprehend.Nevertheless, it proves that many of forms of misleading advertising can harken back to the shadows created by the backlit fire and sculptures in Book VII of Plato’s Republic. Society has alwa ys revolved around art producers and art consumers, just like the puppeteers and prisoners in the cave. Advertising and its respective forms encompass many lessons that we have learned from Plato’s allegory, and perhaps one day humanity will recognize the seemingly inescapable cycle of art production and consumption we are all enveloped in.Only then can we fathom escaping the cave and becoming true philosophers, by having the ability to distinguish imitation from actuality. In conclusion, it is safe to say that there are major implications of the allegory of the Cave on advertisements in our modern society, and thus Plato’s piece will continue to be purposeful for such media centuries to come. Texts: Plato. Republic. Trans. G. M. A Grube. Indianapolis, USA: Hackett Publishing, 1992. Print.

PROJECT MANAGEMENT Essay Example | Topics and Well Written Essays - 750 words

PROJECT MANAGEMENT - Essay Example ontingency to accommodate the risk of incurring unidentifiable but normally occurring costs within the defined scope† (â€Å"What is Cost Baseline,† n.d.). This is referred to as a â€Å"financial plan prepared for every major expense category, such as administrative cost, financing cost, production cost† ( â€Å"Cost Budget†; â€Å"Budget,† n.d.). It essentially contains the list of all planned and expected revenues and expenses which is defined by Sullivan & Sheffrin (2004) as the â€Å"plan for saving and spending.† This is considered as one of the vital plans to be taken up before starting to operate a business because this report helps in the proper allocation of resources, â€Å"evaluates performance and formulates plans† (Ward, n.d.). Cash flow report is also called as the statement of cash flows or funds flow statement (Helfert, 2001). Previous accountants termed this as the flow of funds statement (Bodie, Kane & Marcus, 2004). This report mainly tackles on the change of cash all throughout a business year. The change of cash involves three major categories; operating cash flow, investing cash flow, and financing cash flow (Comiskey & Mulford, 2000). It is further defined by Erich Helfert (2001) as the â€Å"financial statement that shows how changes in balance sheet accounts and income affect cash and cash equivalents, and breaks the analysis down to operating, investing, and financing activities.† This report has been employed by companies because â€Å"it eliminates allocations which might be derived from different accounting methods, such as various timeframes for depreciating fixed assets† (Epstein & Jermakowicz, 2008). This report is usually used by companies to determine â€Å"the costs of multiple resources for all periods during which the resources are available between a specified start and end time† (â€Å"Resource Costs Summary Analysis,† n.d.). It is quite helpful to minimize certain unnecessary expenditures and to find out practical and long-term

PURE Essay Example | Topics and Well Written Essays - 1250 words

PURE - Essay Example Even demand was increasing for raw foods, those that were thermally processed at 120 degrees, which is representative of the planet’s ambient temperature, which was said to aid in digestion, sustain natural healthy bacteria levels, and ensure maximum nutritional content. The main objective was to establish an eatery that would have market-centric relevance, especially in relation to food availability on the menu and the internal decor. Utilizing a naturalistic environment consisting of woods, natural greenery, and a variety of displayed vegan and raw products, Graham and Buob wanted to create legitimate relationships with customers that valued these naturalistic elements supported through knowledge exchanges with consumers in an eco-sustainable environment. By promoting an environment where vegan and natural foods consumption lifestyles could merge with ownership and staff, the objective was to create a revolutionary type of restaurant that could cater to this expanding market niche. The Main Problems at Pure Problems with the foods regulatory environment posed reputational risks for the variety of products that were procured by Pure. The United States Department of Agriculture allowed or five percent of an organic product’s attributes to contain non-organic materials. ... This meant that Pure might not be able to promote products to a holistic niche market since they maintained no control over procurement regulations and would likely not gain the attention of mainstream consumers either. Pure also had to promote a higher pricing model due to the high costs of procurement for organic and vegan products along the supply chain. Mainstream consumers were more attracted to fast food products and packaged/processed foods due to their lower pricing structure. The competitive environment provides many different lower-priced restaurants which would be a hindrance in attempting to appeal to the price-sensitive consumer market segments. Coupled with a mainstream sentiment that vegan and organic products are tasteless and boring related to flavor, it would be very difficult for Pure to attempt to market to the majority of consumer segments, thus being forced to cater to only the niche market segments that legitimately valued natural foods. Furthermore, the growth of availability of organic products at regional grocery stores represented a credible threat of substitutes on the market. Pure was unsure about how the ownership would effectively promote the motivation for dining out to consume natural products when grocery stores made these products widely available, especially important in a market with only 17,000 residents making an average of just under $22,000 annually; below the provincial earnings average. A market environment that is limited in terms of available consumers with legitimate resource restrictions posed a significant threat to the high price model necessary for Pure to remain profitable. These restrictions, coupled with the cultural characteristics in Collingwood to enjoy recreational activities that made

Saving Water Essay Example | Topics and Well Written Essays - 750 words

Saving Water - Essay Example Water scarcity is a big problem now everywhere and the possibility of wars in future for the control of water resources cannot be ruled out. This paper analyses the importance of saving water and the consequences of not doing that. Along with food and oxygen, water is an essential commodity for all living things to sustain their life on this earth. Nobody can sustain their life with the help of food and oxygen alone. Water is necessary for many of the bodily functions. â€Å"Though our Earth is made up of 2/3 water, only 1/100 of that water is drinkable†(Save Water Slogans). In other words, availability of drinking water resources is limited. It should be noted that the population size is growing at alarming rate as time goes on. Thus the demand for drinking water is growing day by day. At the same time available fresh water or drinking water resources are getting polluted because of the injudicious activities of human. These facts clearly suggest that water shortage is going to be a big problem in future unless we take proper actions to save water now. Over-consumption of water leads to the over-consumption of another non-renewable resource, energy. Water in your home must be heated for a number of uses, such as cleaning and bathing, and this takes energy. Additionally, your local water utility must use energy to process and deliver water to your home, so the over-consumption of water requires more energy out of the utility company as well (Csiszar). Water is used for power generation in many countries. Hydroelectric power is one of the major energy sources for many countries. Water flowing through the rivers is stored with the help of dams and this water is used to operate huge turbines for power production. Water may become ineffective for power production after it reaches the ocean. In short, saving or storing of water before it reaches ocean is necessary to solve our water scarcity problems. â€Å"Conserving water reduces the demands to

Various songs between 1830-1960 Assignment Example | Topics and Well Written Essays - 3500 words

Various songs between 1830-1960 - Assignment Example I have listened to Jelly Roll Morton as I like blues and jazz and he plays a mean piano. I like the way the instruments interact. This kind of music reminds me of a book I enjoyed once by Machael Ondatje , Coming Through Slaughter, about a jazz horn player who blew his lip out when he went nuts and played until he could not play any more. La Paloma is an old Mexican folk song I also remember hearing as a child. It is a beautiful melody, and I never expected to hear it played as jazz. I guess the melody lends itself to improvisation. I never thought about it as anything other than a pretty folk song and I sure never dreamed that Jelly Roll Morton ever played it, though I guess it would have been very popular for afternoon parties, a la Stephen Foster. 3. King Oliver's Creole Jazz Band, â€Å"Dipper Mouth Blues† (1923) I have to find more of these guys. I think that’s a real early Louis Armstrong playing the muted trumpet. The clarinetist is really mellow. At the time whe n this was recorded, the music was real, no digital augmentation and I love the complexity of this jazz, but I do with it had the fuller sound of stereo. My ears like the depth of modern recordings. I wonder how they ever got that name. It sounds like the name of a fish. I wonder how much music we missed, because the players were racially segregated? 4. Original Dixieland Jazz Band, â€Å"Tiger Rag† (1917) (on APM CD) I have only heard later versions of this tune, I think by Louis Armstrong’s band,. The chorus is very familiar, but I do not really remember the rest of the music. I went looking and found a version with Art Tatum on piano. I did not know anyone’s fingers could move that fast. 5. Louis Armstrong and the Hot Five, â€Å"West End Blues† (1928) Wow, this is one I had not heard. The rhythm is very regular like for dancing, but the instruments are really clear with solos on the horns. I have not heard many trombone solos. It sounds like a low Dix ieland, with the combined instruments and voice sort of having a conversation. The piano sounds like one that has tacks on the hammers. I think that was called honkey tonk piano. It is a great sound and reminds one of the places where this music was played. I get a vision of taverns, bars and some upper scale clubs playing this music. Great trumpet solo by Louis Armstrong. I have liked some things I heard with him playing, but I did not know he was such a great musician. 6. Jelly Roll Morton, â€Å"Black Bottom Stomp† (1926) It is really great that some people are sharing their old 78 records on Youtube. I would never have heard some of these. This tune really showcases dance rhythm Dixieland. The instruments sound a little strange, like maybe they are using mutes on some of the horns. 7. Guy Lombardo, â€Å"We Just Couldn't Say Goodbye† (lyrics) I heard this by Frank Sinatra, but I like the one by Guy Lombardo better. It has more style. The old Sinatra record is a sim ple dance tune with only an interesting solo on a high pitched xylophone. It is a happy love song., while many of this time were very sad. I guess girls really like sad songs and they bought most of the music. After all, it was girls who wanted to dance in these times. It was an acceptable way to touch. There was no television then, so these radio shows were really popular among middle and higher class people. It was happy entertainment, and I prefer the big band sound. 8. Bing Crosby, â€Å"Out of Nowhere†

Global Fashion Industry with a Focus on Moet Hennessy Louis Vuitton Essay

Global Fashion Industry with a Focus on Moet Hennessy Louis Vuitton - Essay Example The essay "Global Fashion Industry with a Focus on Moet Hennessy Louis Vuitton" examines the industry of fashion. The company owns over sixty brands and some of them, like Veuve Clicquot Ponsardin (1772), Chateau d'Yquem (1593), , Guerlain in 1829, Louis Vuitton (1854), Hennessy (1765), Moà «t et Chandon (1743) the have been in the market since the past two centuries (McCrone, 2006). It operates 5 different category of products including wines and spirits, fashion and leather goods, perfumes and cosmetics, watches and jewelry, and selective retailing. LV had been following a strategy of innovation, differentiation and strategic mergers to become a market leader in the fashion industry (Lent, Tour and Perrin, 2009). The company offers exclusivity and high quality and is driven by the motto of attention to detail to deliver the best quality. It follows a policy of developing a brand image that is shared across its brands and supported by all the activities undertaken by the company. T his report contains an analysis of the macro environment (using PESTEL framework) for the global fashion industry to assess the threats and opportunities that an organization like LV may face. It also contains a micro analysis or industry analysis of the fashion industry to evaluate the business environment and the challenges that LV faces. Finally, an internal strength and weakness analysis is conducted to assess how the strengths of LV can be used to capture the opportunities proffered by the macro and the micro environment., and what it needs to do to overcome its weaknesses in order to combat the threats posed by its business environment.   Finally, the report discusses the current strategy of LV in the light of the SWOT analysis and makes appropriate recommendations.    PESTEL Analysis    Political Environment The fashion industry has seen a revolution in terms of its penetration and reach across the diverse cultures and markets globally (Kapferer and Bastien, 2009). The advent of globalization and liberalization of economies across the world have made it possible for products from one end of the globe to be displayed and bought at the other end. The fashion industry too has seen a rapid proliferation across the borders owing to the political liberalization and increased acceptance of the Western lifestyle by the growing middle class in the developing countries (Kotler and Keller, 2011). The political liberalization on one hand has made it possible for brands like LV to be sold across diverse regions like China, India, Brazil and Africa, while on the other hand there has been an increased political activism at the grassroots level in several countries against high fashion and the trend of consumerism (British Standards Institution, 2011). Foreign brands, especially the luxury brands are often the target of censure and attacks in countries where movements are under way or where there is widespread resistance to liberalization. It can be seen that whi le there is scope for international expansion, there is also a need to understand the local sentiments and culture so that the brands can become acceptable and likable internationally.    Economic Environment The recent financial crisis of 2008-2009 saw the fashion industry too see a slow down in sales and business. Large and popular organizations like the Australian Hrringbone and Centro have posted large losses during the crisis period. In addition to loss of revenues, there was also a potent impact on the trends in the fashion –

Discussion 5 Essay Example | Topics and Well Written Essays - 250 words

Discussion 5 - Essay Example The writer also identifies these mistakes such as male chauvinism and egotistic minds. From these mistakes, Rogers ends his piece of writing by insisting on critical thinking on issues and opinions before making informative decisions. From the start and conclusion of the article, a reader is convinced on critical analysis of the article. (Rogers 333) Rogers employs simple and direct language so as to make it easier for understanding the views passed across. The article inspires change in decision making on daily notions and sometimes uninformed decisions about people and issues. From the writing, words such as communication, differences, and decisions play a significant role in enabling readers understand the article. The article bears repetition of words such as understanding and communication. These words form the foundation of the existence of the article and also the delivery of the message. From this, communication comes out as the main point of discussion. The article comes out enlightening in such a way that my personal judgments are put on test and the urge of making informative decisions comes also in. Communication enables individuals understand each another. On the other hand, through communication, people tend disagreeing on issues and matters without informative decisions. The argument bears similar views and opinions from related texts in that both delve into analysis of how people think and handle ideas and

U.S. Employment Regulations Essay Example | Topics and Well Written Essays - 1250 words - 3

U.S. Employment Regulations - Essay Example The primary goal of the company is to comply with existing American laws regarding employment, as well as to deter and to respond to all kinds of harassment in the workplace. The white paper explains related U.S. employment regulations and discusses implications for the company’s global workplace. Employment Laws This section discusses all critical employment laws. Most of them are obtained from the Employment Law Guide: Laws, Regulations, and Technical Assistance Services of the DOL. Wages and Hours Worked: Minimum Wage and Overtime Pay The Wage and Hour Division (WHD) implements the Fair Labor Standards Act (FLSA). The Act provides policies for minimum wages, overtime pay, recordkeeping, and child labor. It gives exemptions for minimum wage and overtime pay (See Appendix A). The Act obliges employers of covered employees to pay them a minimum wage of not less than $7.25 per hour (DOL, 2004). Youth employees, who are below 20 years of age, may receive a minimum wage of not lo wer than $4.25 an hour, during the first 90 successive calendar days of employment (DOL, 2004). Employers are not allowed to terminate existing employees to hire youth or people whom they can pay the youth minimum wage (DOL, 2004). Furthermore, employers can adopt a piece-rate basis in paying employees, as long as the latter get at least the required minimum hourly wage rate and overtime for hours worked that are more than 40 hours in a workweek (DOL, 2004). In addition, the Act allows the employment of particular individuals at wage rates below the statutory minimum wage, as long as they get certificates from the Department of Labor.

Global Studies Class-Gloabal Diasporas and Cultural Change-the Sikhs Research Paper

Global Studies Class-Gloabal Diasporas and Cultural Change-the Sikhs in the United States - Research Paper Example The cartographers used colors to show this trend; there was a huge red spot from Japan to China indicating Buddhists, then there was a huge dark green spot all over the Middle East, and there was blue over most of Europe and America (Juergensmeyer 3). The point is religious density and demographics do not remain the same. Times change and so do the demographics, people move to different places. Now the dark colors of cartographers are turning light due to the mingling of other religious followers (Juergensmeyer 3). The world has truly turned into a global village. The immigration and migration has seen a tremendous increase over the past 50 years. Traveling has become so easy and people are moving out of their comfort zones for better opportunities. This demographic intermingling of religions is healthy because it has given more understanding to people about others religions. The migration is so prevalent that Los Angeles is the second biggest in terms of population of Iranians and Filipinos (Juergensmeyer 4). The US is a multicultural place. Since the time of Columbuss discovery of the United States, there has been an influx of immigrants from all over the world. Suddenly everyone wanted to migrate to the land of opportunities. The Indian subcontinent has many fertile lands situated alongside ancient rivers. One of these most ancient civilizations on earth are found in North India, more commonly known as the Harappa Mohenjo-Daro. In the region of Punjab when it was not divided between India and Pakistan, there was strong minority of Sikh population. Compared to the huge population of Hindus and Muslims in India, the population of the Sikhs was not as much. They were and still are in minority. The world is known for the globalization of trade and economy but not many people pay attention to the globalization of religion. Religion is a global tool in the sense that it propels people to engage in global

The Pantheon as an Architectural Success Essay Example for Free

The Pantheon as an Architectural Success Essay The Roman Pantheon is the most preserved building in Rome despite all the additions and restorations to its original form. The original Pantheon was built in 27 BC by Marcus Agrippa after the conclusion of the Battle of Actium. The monolithic structure seen in Rome today, however, is no longer the original Pantheon from Agrippa’s time. The 27 BC Pantheon burned down in the historic fire of 80 AD and was completely reconstructed by Emeperor Hadrian in 125 AD with the present day structure. Hadrian, however, attributed the construction to the mind behind the original Pantheon as attested to by the inscription on the portico Hadrian left on the building itself, â€Å"Marcus Agrippa, son of Lucius, in his third consulate, made it.† (Ward-Perkins, 111).   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   The Pantheon continues to amaze thousands of individuals daily. Tourists as well as Roman locals are held enchanted by the buildings faà §ade and dome. The interest stirred up by the Pantheon, however, doesn’t involve just tourists and curious eyes of onlookers. The architectural accomplishment that is the Pantheon has evoked many debates and researches as to its resilience to weathering and time. The Pantheon is a wonder of the modern world, a success story that continues to urge minds of the academe to unlock its secrets. This paper intends to delve into the more physical aspect of the Pantheon and unearth the factors that contribute to the greatness of the structure’s architectural design and composition.   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   The Pantheon exemplifies the best of what the Roman architectural revolution put forth during the first century. The Pantheon has within its frame some of the most advanced innovations Roman architects of the first century could provide. Its construction was made possible through the development and utilization of a new type of expert concrete that is now known as Roman concrete. Roman concrete allowed for buildings and architectural structures that were more curvilinear in form. This is most evident in the Pantheon’s configuration (Mark Hutchinson, 24).   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Roman concrete used material that was very similar to the material used today in making concrete. The difference is seen in the way the Romans utilized these materials. The basic technique employed in Roman construction at that time consisted of only a few steps. First, a semi-fluid substance of lime, pozzolan, and small stones are poured in. Then a layer of stones is put on top this mixture. A second batch of the semi-fluid substance is then poured over which another layer of stones are placed. This technique is generally accepted by those studying Roman architecture. Debate continues, however, regarding the placement of the mortar on whether it was poured or tamped (Herring, 14).   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Roman pozzolan-based concrete proved to be advantageous because of the extra aspects it added to the possibilities of design which were not available with lime mortar. One of these aspects is the fact that Roman pozzolan-based concrete did not need to be dried out for them to set. Roman concrete would set even when immersed. These would also cool relatively faster than lime mortar and had an added factor of increasing compressive strength, although tensile strength was low. (Mainstone, 25)   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   The pozzolan base of Roman concrete, however, was not the only factor that made this material superior to all others available during the time of construction of the Pantheon. There were three other factors that played into the excellence of Roman concrete. Romans were very skilled in choosing the best quality of lime for the concrete. It was essential for them to ensure that only the best quality of materials went in to creating their concrete. The early Roman construction workers were also strict in enforcing that the same relative amounts of materials went into the concrete production process. This was to ensure that the concrete they produced would always have the same first-rate quality. The ratio of water mixed with the cement material was also monitored. The Romans made sure that water was minimal in the mixture. The process of placing and compaction of the mortar was also perfected, ensuring that almost no spaces were present in the aggregate. This was to ensure that the structure for which the concrete was being used would attain the highest possible strength and therefore be one that would last under weathering and other corrosive factors (Herring, 16).   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   The construction of the Pantheon was not a simple task. The yard, from which the blocks used to construct the structure, was located 800 meters away from the actual site of the Pantheon. Delivery of the blocks from the building yard to the construction site must have required many laborers. The distance, however, may have also been counterbalanced by the Tiber River via which most of the blocks must have been shipped. With all the work involved in the construction of the Pantheon, it is certain that care and skill were essential in the construction. Only with extra caution and true skill could a monument such as the Pantheon truly stand and outlast its makers. (Hasselberg, 88)   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Understanding the material which contributed to the strength of the Pantheon is only the first step in understanding the might of its design. Certainly, the Roman Pantheon has lasted the test of time and has undergone the weathering of ages due to the Roman concrete with which it was built. And certainly the Romans ability to come up with a plan for this construction and to follow through with these plans through careful execution and skillful craftsmanship added to this architectural success. However, the monolithic structure has continued on as a great architectural feat through time not only because of its durability but also because of its monumental design. The well-renowned painter of the ceiling of the Sistine chapel, Michelangelo, was one of the many people whose amazement and love for the arts were drawn forth by the Pantheon. He is known to have once described the building as having an â€Å"Angelic and not human design†, a design attributable to the competence and expertise of the ancient Romans (Lugli, 1). The Pantheon’s interior is one of the most concrete examples for the beauty and angelic appeal of the building. The first and most conspicuous aspect of the Pantheon’s interior that invites its visitor to exclaim in wonder is not the walls or ceiling but rather the amount of space that welcomes all to take a step inside. Roman architecture considered space to be something more than just a gap between two objects. Rather, space was considered as a concrete object, as something with volume, with equal weight as the human body. The Pantheon provides modern-day proof of the Roman architects need to place room and make space in the architectural designs of the buildings constructed at that time (Semes, C1.1). The extensive space seen in the Pantheon is not complete to be considered as remarkable if left by itself. It must always be considered with relation to a context, the structures forming the boundary of that space. It is then essential for the Roman architects to ensure that the walls and domed ceiling of the Pantheon will do well to complement the space they wish to portray in the building (Semes, C1.2). In the case of the Pantheon, Roman architects chose a round shape to serve as a boundary of the space within the interior of the Pantheon. The circular shape adds to a feeling that the Pantheon’s interior is indeed spacious. The Pantheon’s walls are ordered by an array of extravagant structures such as the building’s columns, lintels, niches, doorways, and of course the wall itself seen between the earlier mentioned structures. The structures involved in the Pantheon’s walls were not only varied in type but were also varied in terms of the subtypes. The additions to the wall were formed into varying shapes, thus forming subtypes, to add to the intricacy of the beauty of the Pantheon’s interior (Semes, C1.2). Take a moment now to scrutinize one of these features which exists as an aspect of the design of the Pantheon celebrated by contemporary architects as a link to early architectural concepts of beauty. This is seen in the three basic dimensions of the Pantheon’s wall. These three dimensions include the diameter of the columns, the space between each column, and the height of the columns. These dimensions are in the ratio of 1:2:9.5 in the Pantheon. Hermogenes, a popular architect during the Hellenistic age, considered these dimensions and ratio to be the makings of a perfect faà §ade. Vitruvius, the engineer during the 1st century in Rome, is most likely the one to bring to life through the Pantheon the concepts introduced by Hermogenes (Hasselberg, 89).   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   The round wall contains many niches as well creating an impression of the wall containing numerous chambers at different levels. These niches contain some of the most reputable men of the Western world including kings of Italy, popes, and famous painters such as Raphael. All niches as well as openings in the wall are framed by an arch of bricks which serve more than just beautification purposes. These arches add to the support of the wall above the openings and niches and were called relieving arches because of this feature. These arches only went so far as the wall and did not invade the Pantheon’s dome. Creating structural support through the use of relieving arches was very common with Roman architects during the time the Pantheon was built (Lugli, 30). Roman architects showed their prowess by the careful placement of these structures, the columns, the lintels, the niches, the doorways, and the wall itself. They alternated solid structures with spaces creating an interaction between the two which worked to increase the Pantheon’s appeal as an architectural masterpiece. The differing shapes in the structures, therefore, did not give a sense of disorder but rather an overall impression of organization in the face of diversity. The walls and its complementing features thus give an observer’s eyes a feast both as individual pieces and as an integrated whole (Semes, C1.2). One of the most acclaimed features of the Pantheon is its domed ceiling. It is celebrated world-wide for its being built. The Romans were known for their addition of arches in their structures. The creation of the Roman Pantheon’s domed ceiling gives evidence to the development of the Roman architectural concept of arches. Roman architecture evolved to improve the concept of the arch, modifying it and making it more complex with the resulting structure of a dome. The Roman concrete based on pozzolan is acknowledged by many to be the reason for the Roman architects’ success in building a domed ceiling. At the time, the new form of concrete made the construction of the ceiling an accomplishable feat. Lime mortar would not have been an easy material to use in the construction of the Pantheon’s ceiling, thus the use of the new pozzolan-based concrete, which had many features of modern Portland concrete, contributed greatly to the monumental task of building the dome-shaped ceiling. However, there are those who believe that although the concrete is one of the main factors involved in the dome’s success, it is not the only factor. Robert Mark and Paul Hutchinson believe that the concentric stepped rings placed in the outer surface of the Pantheon dome add to the success of the ceiling (26). It is believed that the steven step rings helped to bring stability to the entire structure of the Pantheon by adding to the compression of the structure. This is evidenced by the oculus at the center of the dome which serves as a compression ring. The positioning of the ring or oculus effectively distributes the compression of the structure about this point. The compression ring attests to the skill of the Roman architects and engineers. They not only had the skill and knowledge required to create the colossal Pantheon but they also had the expertise and comprehension of modern engineering to create it in such a way that it would remain standing as a solid and stable structure for a long time.   Many of the imitations of the Pantheon add such stepped rings to the dome of their derivative structures probably for the same purpose of stability and compression. The dome was also a successful architectural feat with the help of the coffering. Coffering is the placing of sunken panels of different shapes in accordance with the structures in the ceiling. This serves aesthetic purposes as well as reinforces structural strength. The dome’s underside was also made stronger with the use of lightweight aggregate in the upper part of the building’s edifice. The aggregate was of lower density than the aggregate used in the lower parts of the building such as the walls, floor and columns. It is evident then that a lot of though went into the creation of the Pantheon’s dome (Mark Huthcinson, 26). Because of the addition of an oculus in the domed ceiling, the Pantheon provides a perfect example of an architect’s use of light to emphasize the appearance of space. The Pantheon’s dome has an oculus or opening in the middle which makes a circular form across the Pantheon’s interior, the floor and the walls. Sunlight streams in through the open oculus and gives an enchanting chiaroscuro effect, a term indicating the alternating effect of light and dark, via the columns and niches in the room (Semes, C1.2). The shadows created by the columns and niches plays with the light coming in from the oculus to create the effect of irregular but successive alternations of brightness agains darkness. However, a simple addition of an opening in a spacious room is not enough to create such a marvel as the Pantheon’s interior. There must always be the consideration of the features within the structure’s interior and how these features would interact with the light. The different materials used in the construction of the Pantheon add to the mystery created by the illumination entering from the opening in the dome’s oculus. The classical interior welcomes the streaming in of light from the sun or perhaps even from the moon. The walls, the columns, the niches and even the arches add to the effect given by the streaming glow from above. The marbles with all its colors, the golden gleams from the ornaments, allow for the light to play inside the Pantheon and create different effects (Semes, C1.2). The columns in the Pantheon’s interior are created with different types of marble. Those in the lower zone are of a material called giallo antico. This is a type of marble that is of a yellowish-orange color. Some of the other columns in the lower zone are made of marble with an off-white color streaked with reddish-purple hues, called pavonazzo. The walls and floor are covered with marble of white, green, and green-gray colors. Although it may seem to one who has not seen the Pantheon up close that these colors would clash and cause quite an unattractive display of shades, this is not the case in the Pantheon. The architects and engineers of the Pantheon were so skilled that even in the mixing of these hues; the Pantheon creates a sense of intricate beauty and intimate splendor. These add to the attraction of the Pantheon’s interior for visiting tourists and even for the locals. The colors are so well balanced that the interior creates a sense of energy and of unity despite the variation (Semes, C1.2). The Pantheon lends this energy to its visitors, encapsulating them in its color-induced aura once they step inside the great structure’s walls. The Pantheon came to be used for different purposes, attesting to the flexibility of its architectural design. Historians speculate that the Pantheon may have been initially used as a dedication to the Roman gods and goddesses worshipped by many at that time. It may also have served an astrological purpose which may have been the reason for the oculus or hole at the rooftop of the Pantheon. The structure continued to served as a church in 608, as a funerary afterwards, and as a place where the busts of artists not laid to rest in the Pantheon were placed (Howell, 34). The end of the Roman civilization signaled the replacement of Roman architectural design. The Dark Ages was a time of little growth in architectural design but new architecture was conceptualized by the succeeding Renaissance minds. If not for structures such as the Pantheon, Roman architecture would have been all but forgotten. Today, many historians, architects and researchers continue to study the Pantheon to try and uncover the secrets lost during the downfall of the Roman Empire. It provides modern architects are now returning to the foundations of classical architecture and the Pantheon is a treasure trove of knowledge regarding classical design. The Pantheon provides these architects with aspects of classical design that are no longer visible in modern structures. It is clear that the Pantheon continues to be a legacy of the skill and capabilities of the Roman architects who made it (Semes, C1.2). Works Cited Lugli, G. â€Å"The Pantheon and Adjacent Structures.† Rome: Giovanni Bardi Publisher, 1971 Hasselberg, Lothar. â€Å"Deciphering a Roman Blueprint.† Scientific American 272 (1995): 84-89 Herring, Ben. â€Å"The Secrets of Roman Concrete.† Constructor Magazine September 2002:13-16 Howell, Peter. â€Å"Pantheons: Transformations of a Monumental Idea.† Apollo Magazine September 2005: 33-36 Mainstone, Rowland. â€Å"Letter On the Structure of the Roman Pantheon.† The Art Bulletin 68 (1986): 673-674 Mark, Robert, and Paul Hutchinson. â€Å"On the Structure of the Roman Pantheon.† The Art Bulletin 68 (1986): 24-34 Semes, Steven. â€Å"Pantheon Inside.† Architecture Week 254 (2005): C1.1-C1.2 Ward-Perkins, J.B. â€Å"Roman Imperial Architecture.† New York: Penguin Books, 1985

Examining the theory of mind hypothesis for autism

Examining the theory of mind hypothesis for autism The Theory of Mind (TofM) hypothesis for autism has been investigated extensively in the last 30 years. This essay will review the literature which examines this theory, considering a wide range of methodological and theoretical approaches. It will be argued that whilst there are several strengths of the theory, the TofM hypothesis cannot account for the non-social symptoms of ASD, and therefore cannot be considered to provide a comprehensive account of the disorder. Cognitive evidence (including a range of TofM tests), theoretical issues, and alternative hypotheses of autism will be considered. What is the Theory of Mind Hypothesis for Autism? The TofM hypothesis of autism was first proposed by Baron-Cohen, Leslie and Frith in 1985. It proposed that individuals with autism lack a TofM, leading them to have specific deficits, such as an inability to partake in pretend play and impairment in social skills. The theory has been controversial since its proposal, with several alternative hypotheses being suggested. Cognitive Evidence The earliest tests of TofM ability often relied heavily on tests of false belief, in which participants are required to understand that other people do not necessarily know (or believe) the same as them. For example, Baron-Cohen, Leslie and Frith (1985) investigated TofM ability in children with autism and children with Downs syndrome, and found those with autism were significantly impaired in their understanding of false belief, suggesting a deficit in TofM ability in autism, and thereby supporting the TofM hypothesis for autism. Similar tests involving false belief, such as those carried out by Happe (1995), have supported findings by Baron-Cohen, Leslie and Frith (1985), providing strong support for the TofM hypothesis of autism. The principle problem in using false belief tests is their reliance on language use. (Bloom and German, 2000). Colle, Baron-Cohen and Hill (2007) investigated concerns that a potential inability to understand language associated with false belief tasks may result in individuals with autism failing these tasks, despite have the TofM ability required to pass tests (e.g. Bloom and German, 2000). They used a non-verbal false belief test to compare the TofM understanding of children with ASD to children with SLI, and found that autistic children have specific deficits in TofM which were not present in the SLI control group. They concluded that previous findings of a TofM deficit by research using standard tests of false belief (e.g. Surian and Leslie, 1999) were unlikely to have been confounded by language ability, thereby revalidating claims made by this research. However, there are other issues associated with the reliability of false belief tasks. For example, Bloom and German (2000) have suggested that a single test of TofM is unlikely to comprehensively test all elements of TofM ability in an individual. Furthermore, whilst research in the field shows the majority of autistic participants fail tests of false belief, a small minority of high-functioning autistic individuals pass the test (e.g. Baron-Cohen, Leslie and Frith, 1985). This has raised questions regarding the ability of false belief tests to recognise subtle deficits in TofM ability potentially shown in the high-functioning autistic population (Rutherford, Baron-Cohen and Wheelwright, 2002). As a result, new research in the field has often focused on using alternative tests of TofM. The Reading the Mind in the Eyes test (Baron-Cohen et al., 2001) is an alternative to false belief tasks, in which participants are required to recognise emotions based on images of a persons eyes. To pass this test, participants must rely on subtle cues indicated in the eyes, thereby indicating ability in mental state understanding, or TofM. Baron-Cohen et al. (2001) used this test to show that individuals with ASD are significantly impaired in their ability to recognise emotions using subtle cues, thereby indicating a deficit in TofM ability. A similar test was used by Rutherford, Baron-Cohen and Wheelwright (2002) and Golan et al. (2007) in which participants were required to establish how a person was feeling after listening to a phrase spoken by that person. This test also indicated social impairments caused by a deficit in TofM ability in ASD, as participants with ASD were significantly impaired in their ability to recognise emotions using vocal cues. Research into TofM ability using the Reading the Mind in the Eyes test is particularly beneficial in supporting the TofM hypothesis. Methodologically, the test does not rely on language comprehension, and therefore passing or failing the test is based purely on TofM ability. Both the Reading the Mind in the Eyes test and the Voice variation are able to detect subtle differences in participants social sensitivity, allowing for deficits to be identified in populations that often pass false belief tasks (such as individuals with high-functioning Autism, Baron-Cohen, Leslie and Frith, 1985), and thereby suggesting the TofM hypothesis is generalisable and universal across the highly varied autistic population. The Faux Pas test was also developed by Baron-Cohen et al. (1999), and assesses recognition of faux pas (defined as being when something is said without consideration of whether the information may be something that the listener does not wish to hear or know, Baron-Cohen et al., 1999). In 2009, Zalla et al. investigated faux pas recognition ability in individuals with Aspergers syndrome using the Faux Pas test, and found these individuals made significantly more errors in detecting faux pas than typically developing individuals, were unable to correctly justify the speakers behaviour and were unable to comprehend the impact of this behaviour. Zalla et al. (2009) concluded that this showed a specific deficit in TofM ability in individuals with ASD. Methodologically, research using tests of faux pas lend strong support for the ToM hypothesis for autism by using an alternative test to false belief tasks. Using faux pas tests helps to revalidate claims made by the theory, which could have been considered questionable if relying purely on false belief tests. As a result, these tests provide strong support for the theory that individuals with autism have deficits in TofM. The TofM hypothesis for autism is also strongly supported by research into joint attention ability in autism (Baron-Cohen, 2009). Evidence suggests that joint attention and TofM ability are linked, such that early joint attention ability is a precursor to TofM ability (e.g. Charman et al., 2000). Furthermore, research has indicated that joint attention skills are significantly impaired in infants with ASD. For example, Charman (2003) investigated joint attention ability in infants (aged 20 months) with autism, and found significant deficits. Charman then assessed the social and communication symptoms of these infants at 42 months, and found that symptom severity was correlated with joint attention disability indicated at 20 months. Colombi et al. (2009) also found that young autistic children show joint attention deficits. As joint attention ability is considered to be a precursor for TofM ability, this suggests that TofM deficits are present from infancy or birth in individuals with ASD. This thereby provides support for the TofM hypothesis as a causal account of autism, by suggesting that a TofM deficit may be a primary deficit. This concept is supported by research into symptom severity and TofM ability. In 2003, Tager-Flusberg et al. used a battery of tests to assess TofM ability and symptom severity in autistic participants, and found that severity of social and communication symptoms was partially explained by TofM impairment. These conclusions imply that TofM deficits are causal in producing the social and communication impairments shown in ASD, thereby supporting claims made by the TofM hypothesis that a deficit causes symptoms associated with the condition. In 2007, Tager-Flusberg presented one of the most comprehensive reviews of the hypothesis to date. She assessed evidence which addressed key issues associated with the theory (for example, why some children pass false belief tasks, and whether a TofM deficit can account for all deficits associated with autism), evaluating a wide range of evidence (including cognitive testing and neurological evidence). She concluded that whilst there is a TofM deficit in autism, the hypothesis cannot account for all deficits in social-affective information processing associated with the condition. The issue raised by Tager-Flusberg (2007) is perhaps the most important weakness in the TofM hypothesis. Whilst the theory provides an explanation for social and communication deficits typically found in ASD (as successful communication skills require TofM ability, Baron-Cohen, 2009), there is no evidence to suggest that a TofM deficit may account for symptoms such as repetitive behaviour, obsessively pursued interests, and dislike of change (Baron-Cohen, 2009). Joseph and Tager-Flusberg (2004) investigated TofM deficits and repetitive behaviour in ASD, and found no correlation between deficits and severity of repetitive symptoms, thereby supporting the suggestion that the TofM hypothesis cannot account for repetitive behaviour. As a result, the theory cannot be considered comprehensive in terms of explaining all possible symptoms associated with autism. Another issue associated with the TofM hypothesis is that individuals with other disorders have also shown deficits in TofM. For example, Brune (2005) found that individuals with schizophrenia showed significant impairment in TofM, and associated impairments in social behaviour and emotion recognition, similar to deficits shown by individuals with autism. The TofM hypothesis for autism provides no explanation for how autistic individuals are unique in their symptoms, when other conditions exist which show similar TofM impairment. A theoretical constraint associated with the TofM hypothesis is the potentially ambiguous nature of the term TofM. The hypothesis is complicated by debates surrounding the nature of TofM ability in typical individuals. The two principle theories of TofM (Theory Theory and Simulation Theory) explain autism in terms of an inability to form thoughts, representations, and hypotheses about the social world (Theory Theory), or alternatively in terms of an inability to simulate the mental states of others (Simulation Theory) (Currie, 1996). Until an absolute theory of TofM can be established, any evidence in support of a TofM hypothesis for autism remains ambiguous in terms of exactly what deficits individuals with autism have (i.e. deficits described by Theory Theory or deficits suggested by Simulation Theory). When considering the literature investigating the TofM hypothesis, it is worthwhile acknowledging the wide body of neurological research. Research in this field provides strong support for a TofM deficit in ASD, with studies such as those by Kana et al. (2009), Mason et al. (2008), and Dapretto et al. (2006) suggesting abnormal brain activation in autistic participants in brain regions associated with TofM. However, research into a neurological basis for autism has also emphasised the issues associated with the TofM hypothesis. For example, Hadjikhani (2007) state that it is unclear whether dysfunction in brain regions associated with TofM could explain behavioural symptoms shown in autism (such as repetitive behaviour and concrete thought), or how structural and functional brain abnormalities originate in autistic individuals. This research highlights the key strengths and weaknesses associated with the TofM hypothesis as a cognitive account of autism, and reinforces cognitive resea rch suggesting the hypothesis cannot be considered as a comprehensive account of the condition. Summary The preceding review provides strong evidence to support a deficit in TofM in autism, which is likely to be present from birth. The review also suggests that symptom severity can be at least partially accounted for by degree of TofM deficit. However, there are significant issues when considering the TofM hypothesis for autism. These issues include an inability of the hypothesis to explain how non-social symptoms can be accounted for by a TofM deficit, a lack of explanation of the significant symptom variability shown in the autistic population, as well as theoretical constraints. Until these issues are addressed, the TofM hypothesis cannot be considered as a comprehensive account of autism. Alternative Theories of Autism The issues associated with the TofM hypothesis led to a range of alternative theories of autism being developed, which must be considered when reviewing literature investigating the TofM hypothesis. One of the first theories to be proposed since the TofM hypothesis was the Executive Dysfunction theory (Ozonoff, Pennington and Rogers, 1991). This theory contradicted the TofM hypothesis, in that it proposed that individuals with autism have deficits in executive function ability (Yerys et al., 2006). This theory became popular in autism research, as the theory appeared to provide more comprehensive accounts of the autistic traits (both social and non-social) presented in these individuals daily (Hill, 2004). Furthermore, a large number of investigations found executive dysfunction in autistic individuals. For example, Ozonoff and McEvoy (2008) examined cognitive development in autistic individuals over a three-year period, and found significant deficits in executive functioning. McEvoy , Rogers and Pennington (2006) also found a deficit in executive functioning in autism. However, recent research has suggested that executive dysfunction may be secondary to the autism. Yerys et al. (2006) investigated executive function in young children with ASD and found no evidence of dysfunction, suggesting that executive dysfunction in adults with ASD has developed gradually and is not a causal factor of the condition. Dawson et al. (2002) also found evidence for normal executive function ability in young autistic children, and concluded that dysfunction found at a later age was a consequence of living with the disorder. As a result, whilst this theory initially appeared to provide a valid and reliable alternative to the TofM hypothesis for autism, there is now strong evidence to refute executive dysfunction as a causal account of autism, and this research cannot be considered to provide evidence to invalidate the TofM hypothesis. A more successful theory was proposed by Baron-Cohen (2008) as a development of the TofM hypothesis of autism. The Empathizing-Systemizing theory proposes that individuals with autism have deficits in understanding others mental states and responding appropriately (empathy), but have an average or above average systemizing ability (i.e. using rules and regularities to analyze and construct systems). As a result, autistic individuals show deficits in social ability (caused by empathy deficits) and non-social symptoms such as repetitive behaviours, obsessively pursued interests, and dislike of change (caused by average or above systemizing ability) (Baron-Cohen, 2009). This theory is particularly successful for several reasons. From a methodological perspective, the theory provides an explanation for both social and non-social symptoms of autism, a key issue in the TofM hypothesis. The theory also explains the uniqueness of autism, such that whilst other conditions may show deficits in empathy (e.g. schizophrenia, Montag et al., 2007), no other condition also shows average or above average systemizing ability (Baron-Cohen, 2009). The theory is also strongly supported by research. For example, Lawson et al. (2004) investigated empathizing and systemizing in participants with ASD and typically developing controls, and found those with ASD were significantly worse at empathizing than controls, but were not significantly different in their ability to systemize. Wakabayashi et al. (2007) found individuals with ASD were impaired in their ability to empathize, but significantly better than typical controls in their ability to systemize. This theory has therefore become a valid and reliable alternative to the TofM hypothesis for autism. Conclusions This essay has reviewed the literature which critically examines the TofM hypothesis for autism. It is clear that whilst there is adequate evidence to suggest a TofM deficit in autistic individuals, the hypothesis cannot account for non-social elements of ASD. New theories of autism must incorporate the concept of TofM deficits, whilst aiming to account for all social and non-social symptoms, as well as symptom variability and severity. A greater emphasis on the understanding how cognitive deficits associated with autism generate the symptoms shown in the condition would have important implications for the development of interventions aimed at improving social skills and symptom management in individuals with autism.

CuH-mediated Hydroamination of Styrene

CuH-mediated Hydroamination of Styrene Abstract: A detailed computational exploration of mechanistic intricacies of the copper(I) hydride (CuH)-catalysed hydroamination of styrene with a prototype hydoxylamine ester by a recently reported (dppbz)CuH catalyst (dppbz ≠¡ {P^P} ≠¡ 1,2-bis(diphenylphosphino)benzene) is presented. A variety of plausible mechanistic avenues have been pursued by means of a sophisticated computational methodology, from which a general understanding of the factors controlling hydroamination catalysis emerged. The catalytically competent {P^P}CuI hydride, which is predominantly present as its dimer, involves in irreversible hydrocupration proceeding with complete 2,1 regioselectivity to form a secondary {P^P}CuI benzyl intermediate. Its interception with benzylamine ester produces the branched tertiary amine product and {P^P}CuI benzoate upon intramolecular SN2 disruption of the amine electrophiles N-O linkage to precede highly rapid, strongly exergonic C-N bond-forming reductive eliminati on. The {P^P}CuI benzoate corresponds to the catalyst resting state and its conversion back into the {P^P}CuI hydride upon transmetalation with a hydrosilane is turnover limiting. The effect of electronic perturbations at the amine electrophile upon the reaction rate for productive hydroamination catalysis and also non-productive reduction of the hydroxylamine ester has been gauged, which unveiled a more fundamental insight into catalytic structure-performance relationships. Introduction The catalytic hydroamination (HA) reaction, the direct addition of an N-H bond across an unsaturated carbon-carbon linkage, offers facile access to an industrially relevant organonitrogen commodity and fine chemicals in a green, waste-free and highly atom-efficient manner.[1] By focusing on late d-block metal catalysis, several distinct mechanistic pathways have been revealed over the years for the hydroamination of alkenes, including the following principal processes: 1) N-H bond activation with subsequent alkene insertion into the metal-NR2 linkage,[2] nucleophilic attack of an amine at a metal-bound alkene,[3] nucleophilic attack of a metal amido species at an activated alkene[4] and amine coordination to be followed by proton transfer onto an activated alkene.[5] Despite the significant progress achieved over the past years the utilisation of these methodologies is still limited by a number of drawbacks.[1] The development of a general approach for regio- and enantioselective hyd roamination of a broad range of alkene substrate classes, in particular, remains an important challenge in the context of intermolecular HA. Recently, the groups of Miura[6] and Buchwald[7a] reported independently a mechanistically distinct approach for styrene HA that involves copper(I) hydride (CuH) as the catalyst together with amine electrophiles and a hydrosilane hydride source to furnish amines in excellent yields and enantio-/regioselectivities under mild conditions.[8] Miura and co-workers disclosed that styrenes react with benzylamine ester reagents in THF at room temperature to afford exclusively branched benzylic tertiary amines in the presence of a (dppbz)CuH catalyst (dppbz ≠¡ {P^P} ≠¡ 1,2-bis(diphenylphosphino)benzene) and a hydrosilane hydride source (Scheme 1).[6] Treatment of the Cu(OAc)2/dppbz starting material with Li(OtBu) and a reducing agent likely gives rise to {P^P}Cu(OtBu) 2, which becomes converted into the catalytically competent {P^P}CuI hydride 3 through transmetalation with silane. According to plausible mechanistic pathways outlined in Scheme 2 styrene insertion into the Cu-H linkage at 3 leads to {P^P}CuI alkyl 4 that couples with the benzylamine ester electrophile thereafter to generate amine product P and {P^P}CuI benzoate 6. Various mechanistic pathways can be envisaged for this transformation,[9] but its precise details remain largely elusive thus far. Transmetalation of 6 with hydrosilane regenerates the catalytically competent {P^P}CuI hydride for another catalyst turnover. The performance of HA catalysis via the productive cycle can be compromised by the well known aptitude of the {P^P}CuI hydride to reduce the amine electrophile. This may proceed through various pathways to involve formation of either N-H (one plausible path via a {P^P}CuIII benzoate amido hydride intermediate 7 is exemplified in Scheme 2) or O-H bonds to afford {P^P}CuI benzoate 6 by consumption of a molar equivalent of the amine electrophile. Precise knowledge of both the operative mechanism and of catalytic structure-performance relationships are indispensable for the rational design of improved HA catalysts. In light of the fact that precise details of mechanistic intricacies of CuH-mediated vinylarene HA remain largely elusive thus far,[10] a sophisticated computational protocol has been employed as an established and predictive means to study reaction mechanisms and to guide rational catalyst design. The present study scrutinises rival mechanistic pathways for HA of styrene (1a ≠¡ S) with O-benzoyl-N,N-dimethyl-hydroxylamine (1b ≠¡ A) by a catalytically competent dppbz-ligated CuI hydride complex in the presence of prototype trimethylsilane (1c ≠¡ H) as hydride source. No structural simplification (other than replacing O-benzoyl-N,N-diethyl-hydroxylamine and HSiPh3 used in experiment by 1b and 1c, respectively, solely for the purpose of computational efficiency) of any kind has been imposed for any of t he key species involved. The computational methodology employed (highly accurate DLPNO-CCSD(T) in conjunction with basis sets of def2-TZVP quality and a sound treatment of bulk solvent effects) simulated authentic reaction conditions adequately and mechanistic analysis is based on Gibbs free-energy profiles. This computational protocol can confidently be expected to reliably map the energy landscape and this has allowed mechanistic conclusions with substantial predictive value to be drawn. As detailed herein, our comprehensive mechanistic examination provides support that effective HA catalysis involves irreversible hydrocupration with strict 2,1 regioselectivity to be followed by generation of the branched tertiary amine product by interception of the thus formed secondary {P^P}CuI benzyl nucleophile with amine electrophile. The prevailing pathway sees the first intramolecular SN2 displacement of the benzoate leaving group and is followed by highly facile and strongly exergonic C-N bond-generating reductive elimination from a highly reactive, intervening {P^P}CuIII species. It leads to amine product and {P^P}CuI benzoate, the latter of which corresponds to the catalyst resting state. Its conversion back into the catalytically competent {P^P}CuI hydride is turnover limiting. Results and Discussion The aim of the present study is twofold. A first part scrutinises thoroughly all the relevant elementary steps of Scheme 2, with special attention devoted to the several mechanistic avenues that can be invoked regarding the interaction of {P^P}CuI alkyl nucleophile with the amine electrophile and also the productivity-limiting reduction of the amine transfer agent. A second part explores the effect of electronic perturbations at the amine electrophile upon catalyst performance. {P^P}CuH-mediated HA of styrene with amine electrophile 1b Catalyst initiation Effective HA catalysis entails the initial conversion of {P^P}Cu(OtBu) 2 into the catalytically competent {P^P}CuI hydride compound. The ability of hydrosilane 1c (≠¡ H) to affect transmetalation at 2, although being rather unlikely turnover limiting, will influence the performance of HA catalysis, since it determines the amount of catalytically competent {P^P}CuI hydride species available for catalyst turnover. Hydroxylamine ester 1b (displaying a slight preference for à ¯Ã‚ Ã‚ «1-N over à ¯Ã‚ Ã‚ «1-O donor ligation) and THF (T) show a comparable aptitude to bind at copper in 2. However, the entropic costs linked with reactant association place the respective adducts 2†¢A, 2†¢T higher in free energy relative to the separated fragments. This gap widens regularly for ever weaker donor molecules as clearly seen in Figure 1 for silane (2†¢H) adducted species. Furthermore, 2 exhibits no propensity toward dimer formation, as all the efforts to localise a dimeric species failed. After the initial facile, but uphill association of trimethylsilane 1c at 2, transmetalation evolves through a metathesis-type transition-state (TS) structure (see Figure S1 in the Supporting Information), which decays thereafter into the {P^P}CuI hydride complex 3 through facile liberation of Me3SiOtBu. Figure 2 reveals an affordable kinetic barrier (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 22.4 kcal mol-1 relative to {2 + 1c}) for conversion of 2 into the catalytically competent complex 3, which is driven by a thermodynamic force of substantial amount. {P^P}CuI hydride compound Reactant (styrene S, hydroxylamine ester A, hydrosilane H), amine product (P) and THF (T) solvent molecules can associate in various ways at copper in the catalytically competent hydride compound (see Figure S2 in the Supporting Information) to give rise to a multitude of adducted species, all of which are expected to participate in mobile association/dissociation equilibria.[11] Similar to what is found for 2, the copper centre can accommodate only a single molecule;[13] its moderate binding enthalpy, however, cannot compensate for the associated entropic costs, thereby rending the various adducted species to be higher in free energy than the respective separated fragments. Amines (A, P) and styrene (benefitting from coppers ability for backbonding) are found to associate preferably and hence 3†¢A, 3†¢S display an energy gap (relative to separated fragments) that is somewhat smaller than for 3†¢T and 3†¢H (Figure 3). On the other hand, 3 exhibits a pronounced pro pensity towards dimer formation with 3dim is favoured by 7.5 kcal mol-1 relative to 3 (Figure 3). Hence, the catalytically competent {P^P}CuI hydride is predominantly present as dimer 3dim with relevant adducts 3†¢S (productive cycle, Scheme 2) and 3†¢A (non-productive cycle, Scheme 2) are well separated and higher in free energy by more than 12 kcal mol-1 (Figure 3). Styrene insertion into the Cu-H linkage Following the plausible catalytic scenario in Scheme 2, the productive cycle entails the first generation of {P^P}CuI alkyl 4. Alternative regioisomeric pathways for migratory C=C bond insertion into the Cu-H à ¯Ã‚ Ã‚ ³-bond commencing from 3†¢S have been examined. The possible participation of another reactant, amine product or solvent molecule has been probed explicitly, but neither encounter, product or TS structures featuring a stable coordination of a spectator molecule could be located.[13] Common to both pathways for 1,2 and 2,1 insertion is the evolution of C-H bond formation through a four-centre planar TS structure describing metal-mediated migratory insertion of the styrene C=C linkage into the polar Cu-H bond, which occurs at distances of 1.57-1.65 Ã… (see Figure S3 in the Supporting Information) for the emerging C-H bond. Following the reaction path further, TS structures decay into primary {P^P}CuI alkyl 4b (1,2 insertion) and secondary {P^P}CuI benzyl 4a (2,1 insertion), respectively. Effective delocalisation of electron density is known to markedly influence the stability of the polarised TS structure describing the interaction of an electron-rich Cu-H à ¯Ã‚ Ã‚ ³-bond with the styrene C=C linkage and also of 4, such that the regioselectivity of the hydrocupration is largely dictated on electronic grounds.[14] The  °-electron-withdrawing arene functionality at the styrene carbon directly adjacent to the copper centre effects an effective depletion of electron density from the nonsubstituted olefinic CH2 centre in the TS structure and also assist through hyperconjugative interaction with the stability of 4a. Hence it electronically stabilises both the TS structure for 2,1 insertion and 4a when compared to the species involved in 1,2 insertion that are devoid of such an opportunity. The located TS and product species (see Figure S3 in the Supporting Information) give no indication that the electronic predisposition towards 2,1 insertion is likely to be reversed due to favourable {P^P}Cu-arene interactions along the 1,2 pathway. Thus, 2,1 insertion is expected to prevail energetically on both kinetic and thermodynamic grounds. Indeed, Figure 4 reveals that migratory olefin insertion proceeds with complete 2,1 regioselectivity to afford secondary {P^P}CuI benzyl 4a by overcoming a barrier of 21.6 kcal mol-1 (à ¯Ã‚ Ã¢â‚¬Å¾G relative to 3dim), whereas the 1,2 pathway remains inaccessible due to higher kinetic demands (à ¯Ã‚ Ã¢â‚¬Å¾Ãƒ ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 4.1 kcal mol-1) and is also disfavoured thermodynamically (à ¯Ã‚ Ã¢â‚¬Å¾Ãƒ ¯Ã‚ Ã¢â‚¬Å¾G = 4.4 kcal mol-1). It characterises hydrocupration via the energetically prevalent 2,1 pathway to be kinetically viable and irreversible.[15] Amine product generation upon interception of 4 by amine electrophile The interception of {P^P}CuI alkyl 4 with amine electrophile 1b gives rise to the generation of amine product P and releases {P^P}CuI benzoate 6 (Scheme 2). Various mechanistic scenarios are conceivable for this transformation,[9] but, unfortunately, virtually no precise details of the operative mechanism are available.[10] This section intends to fill this gap by thoroughly examining several rival pathways. It includes the cleavage of the hydroxylamine ester N-O linkage via: 1) SN2 displacement of the benzoate leaving group; 2) intramolecular SN2 displacement; and 3) oxidative addition across the N-O linkage. This affords transient {P^P}CuIII intermediate 5, from which P and 6 are likely formed upon C-N bond-forming reductive elimination. The generation of the branched tertiary amine product Pa in a single step through nucleophilic attack of the Cu-C linkage at the positive N(amine) centre with concomitant N-O bond cleavage has been probed as a further plausible mechanistic avenue ( dashed arrow in Scheme 2). Given that hydrocupration proceeds with strict 2,1 regioselectivity, the discussion will focus exclusively on pathways that commence from 4a. Notably, rival paths starting from 4b are found energetically non-competitive in every case studied. The full account of all the studied pathways can be found in the Supporting Information. We start with examining N-O bond cleavage of 1b by nucleophilic {P^P}CuI benzyl 4a. Figure 5 collates the free-energy profile of the most accessible pathway for the various mechanistic scenarios examined, whilst structural aspects of key species involved can be found in Figures S4-S9 (see the Supporting Information). The electrophile 1b binds preferably via its N donor centre (à ¯Ã‚ Ã‚ «1-N) at copper to furnish adducts with the unbound carboxylate oxygen pointing either towards (4a1†¢A) or away (4a2†¢A) from the metal, both of which are higher in free energy than the separated fragments. The located TS[4a2†¢A5a] structure describes N-O bond cleavage that is reminiscent of a SN2 displacement of the benzoate group, featuring distances of 1.72 and 2.02 Ã… for vanishing N-O and emerging Cu-N amido bonds (see Figure S5 in the Supporting Information). Progressing further along the reaction trajectory, the benzoate group binds eventually at copper to deliver transient { P^P}CuIII intermediate 5a. The intramolecular process version commencing from 4a1†¢A evolves through a five-centre TS[4a1†¢A-5a] that displays similar metrics regarding vanishing N-O and emerging Cu-N amido bonds, but crucially benefits from an already pre-established Cu-O(benzoate) contact (see Figure S7 in the Supporting Information). As it turns out, this contact likely renders 4a1†¢A→5a intramolecular SN2 displacement somewhat favourable kinetically over 4a2†¢A→5a with both pathways are indistinguishable on thermodynamic grounds. The TSOA[4a2†¢A-5a] shown in Figure 5 (see also Figure S9 in the Supporting Information) has been located as energetically prevalent three-centre TS structure describing oxidative addition across the N-O linkage that occurs at distances of 2.43 Ã… and 1.89/2.60 Ã… for vanishing N-O and newly built Cu-N(amido)/Cu-O bonds, respectively. The condensed free-energy profiles in Figure 5 reveal that for cleavage of the electrophiles N-O linkage by {P^P}CuI benzyl nucleophile the 4a1†¢A→5a intramolecular SN2 pathway (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 19.8 kcal mol-1 relative to {4a+1b}) prevails kinetically somewhat over 4a2†¢A→5a, with oxidative addition proceeding through TSOA[4a2†¢A-5a] (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 31.1 kcal mol-1 relative to {4a+1b}) is found substantially more demanding kinetically and hence not accessible. The fine energy balance between the alternative SN2-type pathways is likely be influenced by the diphosphine catalyst backbone. Figure 6 combines the dominant pathway for N-O bond cleavage at amine adduct 4a†¢A with C-N bond-generating reductive elimination at transient {P^P}CuIII 5a taking place thereafter. Given that benzyl and amido functionalities are already preferably arranged in 5a no major structural reorganisation is required prior to traversing TS[5a6†¢Pa], which occurs at a distance of 2.36 Ã… of the emerging C-N bond (see Figure S11 in the Supporting Information) and decays thereafter into the branched tertiary amine product that is initially bound to {P^P}CuI benzoate (6†¢Pa), but is readily released thereafter. The reductive elimination is found highly facile (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 5.2 kcal mol-1 relative to 5a) and driven by a remarkably strong thermodynamic force (Figure 6). Of the two consecutive steps converting {P^P}CuI benzyl 4a into amine product Pa and {P^P}CuI benzoate 6 through interception with electrophile 1b, the first intramolecular SN2 displacement of the ben zoate leaving group determines the overall kinetic demands (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 19.8 kcal mol-1 relative to {4a+1b}) with Pa and 6 are then generated from transient, highly reactive {P^P}CuIII intermediate 5 upon rapid and strongly downhill reductive elimination. Nucleophilic attack of the Cu-C linkage at the positive N centre of the amine electrophile with concomitant N-O cleavage, thereby affording 6a + Pa in a single step, describes an alternative mechanistic scenario. Despite all our efforts, a precise TS structure associated to this pathway could not be located, but examination by means of a state-of-the-art reaction-path-optimisation (chain-of-state; see the Computational Methodology) method provided a reasonably approximate TS structure. The multicentre TS[4a1†¢A-6†¢Pa] describes concerted N-O bond cleavage (2.30 Ã…) together with C-N (2.54 Ã…)/Cu-O(2.37 Ã…) bond formation, all occurring in the immediate vicinity of the copper centre (see Figure S12 in the Supporting Information). A substantial barrier of approximately 30.7 kcal mol-1 (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ relative to {4a+1b}) has to be overcome (Figure 7), which renders the concerted 4a1†¢A→6†¢Pa pathway non-accessible kinetically in the presence of the viable two-step conversion shown in Figure 6.[16] {P^P}CuI benzoate compound In light of the strong thermodynamic force associated with generating the C-N bond, the {P^P}CuI benzoate may become, among others, a candidate for the catalyst resting state. Hence, the aptitude of 6 to accommodate additional reactant, amine product and THF solvent molecules has been probed in order to clarify its precise identity. In accordance with findings for 2 and 3, a single molecule only can bind at copper at the expense of one of the two Cu-O(carboxylate) linkages, but adduct formation is disfavoured in terms of free energy. Hence the {P^P}CuI benzoate is predominantly present as non-adducted form 6 featuring a à ¯Ã‚ Ã‚ «2-O ligated benzoate functionality (Figure 8). Regeneration of {P^P}CuI hydride from {P^P}CuI benzoate Transmetalation of 6 with trimethylsilane 1c regenerates the catalytically competent {P^P}CuI hydride 3 for another catalyst turnover, thereby closing the cycle for productive HA catalysis. Two scenarios have been analysed that are distinguished by which of the carboxylate oxygens at silane adducted 6†¢H participate in Si-O bond formation. The transfer of silyl onto the oxygen directly bound to Cu evolves through a four-centre metathesis-type TS[6†¢H-3†¢OS1] and leads eventually to 3 upon facile liberation of Me3SiOBz. On the other hand, a six-centre TS[6†¢H-3†¢OS2] is traversed along an alternative pathway representing silyl transfer onto the unbound carboxylate oxygen (Figure 9 and Figure S13 in the Supporting Information). The enhanced stability of six-centre TS[6†¢H-3†¢OS2] versus four-centre TS[6†¢H-3†¢OS1] discriminates among the two pathways, which are driven by a thermodynamic force (à ¯Ã‚ Ã¢â‚¬Å¾G = 0.5 kcal mol-1 relative to {6 + 1c}) of identical magnitude. The assessed barrier of 26.2 kcal mol-1 (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ relative to {6 + 1c}) for the most accessible pathway characterises 6 + 1c→3 + Me3SiOBz as a kinetically demanding, but viable transformation that is slightly uphill thermodynamically (Figure 9). Reduction of the benzylamine ester by {P^P}CuI hydride The well known tendency of the catalytically competent {P^P}CuI hydride to reduce the amine electrophile under N-H bond formation, hence giving rise to {P^P}CuI benzoate, or alternatively via O-H bond formation to afford a {P^P}CuI amido can severely compromise the catalyst performance. To this end, several conceivable pathways (some of which are sketched in Scheme 2) have been studied. Whilst focusing on thermodynamic aspects amine reduction with N-H bond formation via 3 + 1b→6 + HNMe2 (à ¯Ã‚ Ã¢â‚¬Å¾G = -71.9 kcal mol-1) appears to be strongly favoured over O-H bond generating 3 + 1b→{P^P}CuI(NMe2) + benzoic acid (à ¯Ã‚ Ã¢â‚¬Å¾G = -51.3 kcal mol-1). The cleavage of the N-O linkage of 1b at amine adduct 3†¢A does preferably proceed through SN2 displacement of the benzoate leaving group with the intramolecular pathway proved to be somewhat favourable energetically (see Figure S14 in the Supporting Information), whilst oxidative addition of electrophile 1b across the N-O linkage is found substantially more demanding kinetically. All these aspects closely parallel the findings regarding the preferable avenue that leads to generate {P^P}CuIII 5a (see above). Likewise, N-H bond-forming reductive elimination at {P^P}CuIII amido hydride intermediate 7 is highly facile kinetically and strongly downhill as 5a→6a + Pa is. Unfortunately, all the efforts to localise the associated TS structure have not been successful, but the examination of the reaction path thoroughly by means of a chain-of-state method firmly indicates that reductive amine elimination at 7 has an only marginal barrier, if at all, to overcome, hence it proceeds almost instantaneously. Overall, a smooth, kinetically affordable pathway for undesired 3 + 1b→6 + HNMe2 conversion has been located that comprises a first intramolecular SN2 cleavage of the N-O bond (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 26.3 kcal mol-1 relative to 3dim, Figure 10), to be followed by highly rapid reductiv e amine elimination from an intervening and highly reactive {P^P}CuIII intermediate 7, thus reflecting the well-documented aptitude of 3 to engage in performance-limiting reduction of the electrophilic amination reagent.[6, 7] Further attempts devoted upon locating a proper TS structure for the concerted attack of the nucleophilic Cu-H linkage at the N centre of the amine electrophile to be accompanied with N-O bond disruption has not been successful. However, a reasonably approximate TS (see Figure S15 in the Supporting Information) is seen to be above TS[31†¢A-7] by another 19.8 kcal mol-1, such that the concerted pathway can confidently be discarded as energetically viable alternative to the operative two-step process. Proposed catalytic cycle The mechanistic picture based upon the above thoroughly conducted examination of relevant elementary steps is presented in Scheme 3. An energetically smooth and downhill sequence of steps transforms the starting material into the catalytically competent {P^P}CuI hydride 3, which is in a mobile equilibrium[11b] with its thermodynamically prevalent dimer 3dim. Migratory insertion of the styrene C=C linkage into the Cu-H bond is kinetically facile (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 21.6 kcal mol-1 relative to { ½3dim+1a}), thermodynamically downhill and proceeds with strict 2,1 regioselectivity. Hence irreversible hydrocupration is regioselectivity determining and occurs prior to the turnover-limiting step. The interception of the thus generated secondary {P^P}CuI benzyl 4a with amine electrophile 1b produces the branched tertiary (Markovnikov) amine product Pa and {P^P}CuI benzoate 6. This transformation favours a two-step process comprising the first intramolecular SN2 displacement of the b enzoate leaving group (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 19.8 kcal mol-1 relative to { ½3dim+1a+1b}) to furnish transient, highly reactive {P^P}CuIII intermediate 5 from which Pa and 6 are generated upon highly rapid and strongly downhill reductive elimination. It renders 6 to be the most stable species of the cycle for productive HA catalysis and it thus corresponds to the catalyst resting state. The regeneration of catalytically competent 3 from 6 through transmetalation with hydrosilane 1c is found most demanding, but affordable, kinetically (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 26.2 kcal mol-1 relative to {6+1c}) and hence is turnover limiting its assessed barrier is compatible with reported catalyst performance data.[6] It is worth mentioning that a similar picture regarding hydrocupration and transmetalation steps has emerged from a recent experimental study by the Buchwald group on a DTBM-SEGPHOS-based CuI catalyst.[7d] A stepwise pathway closely related to 4a†¢A→6 + Pa is preferably traversed for the non-productive reduction of amine electrophile by 3. An intramolecular SN2 N-O bond disruption (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 26.3 kcal mol-1 relative to { ½3dim+1b}) precedes highly facile and strongly downhill reductive amine elimination from intervening, highly reactive {P^P}CuIII intermediate 5a. The assessed small kinetic gap (à ¯Ã‚ Ã¢â‚¬Å¾Ãƒ ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 0.1 kcal mol-1) between discriminative TS structures for productive and non-productive reaction branches reflects adequately the observed close competition between the two processes, which can lead to compromised catalyst performance for improper chosen amine electrophiles. Furthermore, it provides further confidence into the substantial predictive ability of the herein employed high-level computational methodology.[17] Effect of the amine electrophile upon catalyst performance A second part of this study explores the effect of the amine electrophile upon catalyst performance. To this end, the energy profile for two