Epistemology and Skepticism Essay Example for Free

Epistemology and Skepticism Essay * Epistemology and Skepticism: How does The Matrix outline the test of distrust about the outer world? Clarify, talk about, and fundamentally assess the mental trip contention for complete epistemological distrust. Be certain your paper incorporates a conversation of either Hospers or Crumley IIs analysis of complete epistemological suspicion. Is finished epistemological distrust an intelligently sound hypothesis? Bolster your answer with an all around contemplated contention liberated from any significant mistakes of certainty, false notion or legitimate logical inconsistency. I. Presentation * The network addresses the idea of the real world * How would we be able to know for sure that the world is how we see it and not only a shroud over our eyes? * Explain film caught in virtual world accepting they are in 21st century * Explanation proposes question, what is genuine? II. Central matters. * Main Character Morpheus: â€Å"What is ‘real’? How would you characterize ‘real’? In the event that genuine is basically what you can feel, smell, taste and see, at that point ‘real’ is essentially electrical signs deciphered by your brain.† * Consequently, â€Å"How would we be able to be certain our mind isn’t being deceived by some reenactment to accept things are genuine, when they aren’t? This is the way framework proposes the test of epistemological incredulity. * Hallucination contention: Modus Tollens, question adequacy (legitimate) 1. On the off chance that we groups information (K) we should have the option to preclude the chance of efficient mind flight (S). K S 2. ~S (the lattice theory.) (MT 1) 3. ~ K ( MT 1 2) * One arguer against wariness: John Hospers * Merely verbal * Skeptics take solid feeling of the word information, must have confirmation consistently * Others utilize powerless sense, which means we possibly need verification or proof just when somebody is demonstrating something else. * Doubt is an unfilled word * Basic point: when a test has been never really question we have a valid justification to trust it is valid, in this way we have information. III. End * Skeptics accept information is absurd, for this situation the mind flight contention demonstrates the premises are valid through Modus Tollens. In spite of the fact that the contention is sound, it is pointless on the grounds that doubters accept they realize that they don’t truly â€Å"know† anything. Also, complete epistemological doubt is certifiably not an intelligently lucid view on the grounds that the contention being asserted would require the individual to have information to direct such contention.

Using the literature about IMC Essay Example | Topics and Well Written Essays - 1250 words

Utilizing the writing about IMC - Essay Example The report has been set up for showing different methodologies towards the utilization of IMC instruments by the advertisers of low inclusion and high contribution items. Its point was to assess the distinction in system age through IMC apparatuses by the advertisers. It has been discovered from the report conversation that the consumers’ view of any item is a definitive initiator for picking the IMC apparatuses. The advertisers of low association items are less keen on utilizing the IMC apparatuses because of the failure of the technique relating to affecting the clients while then again, the advertisers of high contribution items are exceptionally aware of choosing the best IMC devices on the grounds that these systems have been end up being powerful in impacting the clients of high inclusion items over a significant stretch of time.The most significant part of both item just as administration showcasing is to make viable correspondence with clients. The associations which c an viably and effectively speak with their separate purposes to the clients, turns out to be at last fruitful in accomplishing the organisation’s goals. Advertisers utilize showcasing specialized devices for most adequately arriving at their focused on clients. In the current occasions, Integrated Marketing Communication (IMC) approach has created and the advertiser presumes it to be the best among all other individual methods for showcasing communication.... trategy for Relationship Building The idea of Integrated Marketing Communication has picked up its significance as a successful methods for correspondence in the ongoing occasions because of its powerful believability of making long haul relationship with clients. As indicated by the writing introduced by Perkins and Algren (2008), advertisers who have the target of improving relationship with their supporters are increasingly plausible of making progress using IMC devices than the individuals who have lesser worry for relationship building. The possibility of relationship building system is improved through fruitful correspondence of authoritative points and destinations to the clients. Correspondence of the points and destinations is pointed towards production of more noteworthy worth impression of the association among the clients. Since the quality of relationship decides an organization’s age, advertisers, in the advanced world are totally centered around working up long haul relationship with their partners. This writing has been remembered for this report since this will give a premise to additionally investigating the marketer’s perspective in regards to promoting of low association and high contribution items. It can, in any case, be refered to that relationship building is the essential target of utilizing IMC devices by the advertisers (Perkins and Algren, 2008). IMC Tools Used by Marketers of Low-Involvement Products Kitchen and Pelsmacker (2004) in their book â€Å"Integrated Marketing Communication: a Primer† have expounded on the way that it doesn't make a difference concerning what a promotion give to the individuals yet it is important with respect to how the individuals see the commercial. Individuals are keen on investing their significant energy watching notices of those items just which they see to hold an

Courage in to Kill a Mockingbird free essay sample

One gets a kick out of the chance to think about a legend, as solid, bold, and meeting all difficulties head on. All the characters in this book have an alternate view with regards to what boldness is, and they all show it in various manners through their regular day to day existences. More youthful characters, similar to Jem and Scout, see its physical part, though Atticus accepts this to be a very frail type of fortitude. He has confidence in the psychological nature of mental fortitude. The capacity to be in minority and not withdraw and to have the option to transform; he appreciates Mrs. Dubose for her demonstrations of fearlessness that are despite seemingly insurmountable opposition. For a more youthful character, similar to Scout, fortitude is regularly connected with a physical demonstration that is typically perilous. It is difficult for little youngsters to understand that boldness can be appeared in different parts of life. Scout sees a case of boldness in her dad when he shoots the frantic canine Tim Johnson (pg. 101). In spite of the fact that Atticus doesn't consider it extremely gallant, Jem and Scout are glad for their dad and the boldness he appeared in this risky circumstance. Atticus sees mental fortitude on an increasingly learned level, as an ethical thing not something that can be demonstrated with a weapon. Later on in the story, Jem and Scout experience the malevolent, angry Mrs. Dubose who frequently yells out prejudice coordinated at the passing youngsters in view of Atticus’ work. At a certain point she broadcasted, Your dads no better than the niggers and junk he works for! (pg. 111). At the point when she conspicuously made Atticus an object of scorn that way, Jem concluded that the most ideal approach to settle things was to demolish Mrs. Duboses camellias. Since he was unable to assault Mrs. Dubose straightforwardly, Jem chose to go for something near her. He is submitting a physical demonstration of counter, which prompted her enduring mental torment once more. It was a weak demonstration, for he challenged not step up and face her. After Atticus found out about this trick, Jem was made to peruse to all her evenings for a month. He currently required mental valor, and he found it more hard to source this than the physical dauntlessness he was accustomed to showing. This is made clear by him declining to stroll past her home alone, and in light of the fact that Jem was from the outset unnerved of going to see her. Mrs. Dubose was an exceptionally wiped out lady, and had utilized morphine to facilitate her torment yet was currently dependent. It was her objective to leave the world under obligation to nothing and no one (pg. 120). She showed what Atticus alludes to as genuine fearlessness. (pg. 121). She demonstrated genuine fortitude since she doesn't have the advantage of remaining there with a firearm pointed at her fixation. One single endeavor couldn't liberate her from the habit. Or maybe, it must be a many arranged procedure over an all-encompassing timeframe. It was shear assurance and genuine fearlessness that permitted her to achieve her objective. It was not until after she kicked the bucket that Atticus disclosed to Jem and Scout how bold the lady was on the grounds that she realized she was passing on yet was despite everything resolved to bite the dust liberated from the morphine. She battled against extraordinary chances, despite the fact that she realized that she would without a doubt bite the dust. Atticus tells his youngsters that he needed them to perceive what genuine boldness is, rather than getting the possibility that mental fortitude is a man with a firearm in his grasp. He additionally says that she was the most courageous individual he at any point knew. (pg. 121) Real mental fortitude is the point at which you battle for what is correct whether or not you win or lose. Atticus Finch shows genuine mental fortitude a few times all through the novel, notwithstanding the exercises that he shows his kids. The biggest and most significant model would be the preliminary of Tom Robinson. At the point when Atticus took the case, he went facing Maycomb, a for the most part preferential town, so as to guard Tom. He comprehended that taking the case would make him an object of scorn and that nobody would excuse him for accepting a dark keeps an eye on word over a white keeps an eye on. Indeed, even his own sister communicates objection at his choice, for all intents and purposes revealing to him he was carrying disfavor to the family. By and by, regardless of how much his notoriety endured, he didn't adjust his perspective. Defending his ethics and morals was a higher priority than people's opinion of him. From the very beginning Atticus realizes he won't win the case anyway he carries out his responsibility and completions what he set out to do. Atticuss solid feeling of ethical quality and equity propels him to shield Tom Robinson earnestly, giving everything he has. He shows this when he says, Simply in light of the fact that we were licked a hundred years before we began is no explanation behind us not to attempt to win. (pg. 82). He says this to Scout after she returns home from school furious at Cecil Jacobs for ridiculing Atticus in the schoolyard. Atticus advises her to battle with her head rather than her clench hands. He needs the individuals of Maycomb to hear reality with regards to Tom, That kid may go to the seat, yet hes not going till the certainties told. (pg. 159). Atticus is putting everything a man holds dear, nobility, regard, respect and status, on the line to secure Tom. He later shows more boldness when he goes to the prison to shield Tom from a crowd. Without reconsidering, he hurried to Toms help. He went energetically, realizing that if a horde formed he would be extraordinarily dwarfed and would effectively be beaten. All things considered, he put Toms prosperity in front of his own government assistance. While serving equity, Atticus additionally demonstrated incredible fortitude. For instance, he didn't oblige Heck Tate when he lied about what truly happened the night Bob Ewell was found wounded to death. Atticus put his life and profession at risk since he realized that, as an official of the court, denying data of an examination could have gotten Mr. Tate tossed into prison. In any case, in the same way as other occasions previously, making the right decision and reasonable won in Atticuss perspective. Likewise, Atticus conflicted with his ethical code and standards he had consistently maintained previously, when Atticus is confronted with the choice of submitting to the law or breaking it so as to make the best choice. He realized that imprisoning a man like Arthur Radley would have been reprehensible, particularly after Arthur had quite recently played out an extraordinary deed by sparing his childrens lives. He realized that uncovering him would be a terrible method of reimbursing him; it would have been similar to shooting a mockingbird. Thusly, Atticus decided to shield Boo from the open eye as opposed to submit to the law and his legitimate legal ways he was so acquainted with follow. Now and again it takes much more fortitude to set another degree of ethics than to remain in one’s safe place. (pg. 297-302). The boldness to change propensities and musings is significant, on the grounds that not every person can do it. An awesome case of this fortitude is when Atticus asked Scout not to battle any longer. At the point when I subscribed to this demonstration of weakness. Word got around that Scout Finch wouldn’t battle any longer, her daddy wouldn’t let her. (pg. 97). That was an incredible demonstration of mental fortitude since Scout used to battle a ton however as she had guaranteed her dad she would not battle any longer. Scout, similar to Jem wouldn't like to disillusion Atticus, so she rolls out an improvement. All in all, Atticus shows commendable fortitude and conduct in numerous occurrences all through the story, not by battling or murdering, however by going to bat for what he had confidence in an edified and decided manner. His most grounded inspiration, be that as it may, were his kids. He needs to be a genuine model for his children and support in them a solid feeling of virtue. Once Scout asks him for what reason he had taken a case he realized he was not going to win and he reacted by saying, For various reasons. The principle one is, on the off chance that I didnt I couldnt hold up my head around, I couldnt speak to this region in the assembly, I couldnt even let you know or Jem not to accomplish something once more. (pg. 82). As it were, he would not have had the option to converse with his children about equity and supporting what one accepts when he himself had not represented what he put stock in. The exercises educated by Atticus and Mrs. Dubose demonstrate Jem and Scout what it is to be gallant, to have the option to change, to come clean and in particular to go to bat for their own convictions. All qoutes from Lee, Harper, 1960, To slaughter a Mokingbird, London, Pan Books

Brahmanism For Beginners

Brahmanism For Beginners Brahmanism,â also known as Proto-Hinduism, was an early religion in the Indian sub-landmass that depended on Vedic composition. It is viewed as an early type of Hinduism. Vedic composing alludes to the Vedas, the psalms of the Aryans, who in the event that they really did as such, attacked in the second thousand years B.C. Else, they were the inhabitant nobles. In Brahmanism, the Brahmins, who included clerics, played out the hallowed workplaces required in the Vedas.â The Highest Caste This complex conciliatory religion rose in 900 B.C. The solid Brahman force and ministers who have lived and imparted to the Brahman peopleâ included an Indian culture station where just individuals from the most noteworthy rank had the option to become clerics. While there are different standings, for example, the Kshatriyas, Vaishyas, and the Shudras, the Brahmins incorporate clerics who instruct and keep up consecrated information on the religion. One huge custom that happens with nearby Brahman guys, that are a piece of this social standing, incorporates serenades, supplications, and psalms. This custom happens in Kerala in South India where the language is obscure, with words and sentences being misconstrued by even the Brahmans themselves. In spite of this, the ceremonial has been a piece of the male culture in ages for over 10,000 years. Convictions and Hinduism The confidence in one genuine God, Brahman, is at the center of the Hinduism religion. The incomparable soul is praised through the imagery of the Om. The focal act of Brahmanism is penance while Moksha, the freedom, joy and unification with the Godhead, is the fundamental strategic. While the wording shifts by the strict philosopher, Brahmanism is viewed as the predecessorâ of Hinduism. It is viewed as something very similar because of the Hindus getting their name from the Indus River where the Aryans played out the Vedas. Mystical Spirituality Transcendentalism is a focal idea to the Brahmanism conviction framework. The thought is that That which existed before the making of the universe, which comprises the entirety of the presence from that point, and into which the universe will break up into, trailed by comparable perpetual creation-upkeep obliteration cycles as indicated by Sir Monier Monier-Williams in BrÄ hmanism and HindÃ… «ism. This sort of otherworldliness tries to comprehend what is above or rises above the physical condition we live in. It investigates life on earth and in soul and obtains knowledgeâ about human character, how the psyche works and cooperation with people.â Rebirth The Brahmans put stock in resurrection and Karma, as indicated by early messages from the Vedas. In Brahminism and Hinduism, a spirit resurrects on earth over and over and in the long run changes into an ideal soul, rejoining with the Source. Rebirth can occur through a few bodies, structures, births, and passings before getting great. Sources From Brahmanism to Hinduism: Negotiating the Myth of the Great Tradition, by Vijay Nath. Social Scientist, Vol. 29, No. 3/4 (Mar. - Apr. 2001), pp. 19-50.

Taxation Law Capital Gains and Losses

Question Examine about theTaxation Lawfor Capital Gains and Losses. Answer: Presentation Section 1 of the Task Count of Freds net capital increase for the present year, accepting that he has got net capital shortfall from the earlier year of $ 10, 000 emerging from offer of offers This paper is around one Fred who is referenced as an occupant who made climb to an agreement so as to sell his home that was worked in Blue Mountains at around the long stretch of August the earlier year. The offer of the house was finished early this year and the referenced individual got a complete money of $ 800,000 from the buyer (Chen 2012). It is additionally referenced that a legitimate expenses of $ 1100 that is comprehensive of GST was brought about just as the commission of realtor that was similarly comprehensive of GST at $9,900 corresponding to the deal. It is likewise caught that, at around March 1987, Fred bought the home that he sold the earlier year for $ 100,000 and furthermore offered an extra measure of $ 2,000 in stamp obligation on the exchange. Other than the referenced exchanges in the month in setting in 1987, there was additionally $ 1000 that was paid as lawful charges to discover the homes security from the administration. Towards 1990, a manufacturer was locked in by Fred to construct a carport inside a similar home region at $ 20,000. Computation of Freds net capital addition for the present year, and furthermore accepting that he likewise acquired a net capital deficit from the earlier year of $ 10,000 that emerged from the two deals and offers (Faris 2003) Net capital addition is gotten from capital addition, this specific region, is predominantly worried about increment in the estimation of capital for instance, as in the inquiry in setting, there is a capital resource of a place of Fred (Kang et al 2010). For us to plainly comprehend the idea of capital addition, at that point the estimation of the capital resource must be of a higher incentive than the cost of procurement. Since the inquiry in setting is pegged to net capital deficit also, it is crucial for the idea of net capital shortfall or by and large capital deficit to be welcomed on board before any count. A capital misfortune is the total of cash that is brought about when there is devaluation regarding the estimation of the capital resource in contrast with an advantages buy esteem (Karinga 2015). This means, at the hour of offer of a specific capital resource, the incentive to which it is sold or offered in the market is not exactly the worth that was utilized when the benefit in setting was being bought. On a similar note, capital additions can be talked about to for the most part have a relationship with the two assets and stock fundamentally on account of inalienable value unpredictability, similarly as referenced already; its event can be on security that is sold for a measure of cash that is higher than the price tag that was given at the hour of procurement (Kierulff et al 2015) By the by, concerning the talk takes note of that we took in class, it is unmistakably referenced under the arrangements of the Income Tax Assessment Act of 1936, segment 24 AX, it is plainly referenced that there are various rules and methods to be followed or given contemplations when in conversation of the subject (Kubtov 2009). The arrangement in setting goes further to specify that through the idea of net capital increase, there is additionally the capital increase charge that should be made on the capital increase that is made on removal of any benefit or capital resource, with the exception of at times that are likewise accommodated in the arrangements under the Income Tax Assessment Act of 1936. The generally talked about special case that can be made with respect to the CGT is essentially in that of family home yet more subtleties will be clarified in the computation part of the inquiry in conversation. In the event of computing net capital increase, it is imperative to place into thought various key focuses. The primary point is on first affirming that the capital resources esteem is higher than the underlying buy esteem. For instance, the contextual investigation in setting plots the estimation of the capital resource as $ 800,000 which is viewed as high dependent on the grounds that the underlying acquisition of the home of the house was $ 100,000 by March 1987. Another significant key point that must be welcomed on board is the all out capital misfortunes that likewise incorporate net capital misfortunes from the earlier year. The last key thought that ought not be forgotten about is on the CGT markdown and any CGT concessions that one is qualified for (Kneeland 2005). In this way, the absolute capital additions with respect to the year in setting is $ 800,000, this depends on the capital resource. The capital increases of the present year will incorporate deduction of the lawful charges that caught the GST and furthermore the commission that was paid to the realtor. The last capital increase for the present year is will be $ 800, 000-($ 1100+ $ 9,900) = $ 789,000. In the count of net capital increase for the present year, we should incorporate all the costs that were acquired and furthermore welcoming on board the capital shortfall. As indicated by the contextual investigation in setting, all the capital misfortunes will incorporate all the exchanges that were done beforehand. They incorporate the sum at which the capital resource was purchased which was $ 100,000 and extra measures of $ 2,000 which was paid for stamp obligation on the exchange and $ 1, 000 legitimate charges. The referenced subject additionally welcomes on board the cost that was brought about when assembling the carport (McElhany 2014). The cost gauge is evaluated to be $ 20,000. Without the capital misfortune that was referenced for the situation study, first the findings that should be incorporated are as determined, $ (100,000 + 2000 + 1000 + 20,000) = $ 123,000. At the point when net capital deficit is brought into picture, it can either be added to the past total outcomes or we can apply either the CGT markdown strategy or the indexation technique to think of the outcomes (Mundstock 2013). For this situation we will apply the CGT rebate strategy which is as clarified; Capital continues = $ 789,000 Less expense base= $123,000 Capital gain= $666,000 Less capital loss= $ 10,000 Net capital gain= $ 656,000 Part B of Question 1 Regardless of whether My Answer Would Show Difference if the Rose that Came Out from the Sale of an Antique Vase On the off chance that the appropriate response gave in the point by point some portion of the assignment above was from old fashioned container, there would be no distinction since this was not going to end or influence figures and the arrangements that accommodate the capital addition and capital misfortune under ITAA of 1936 (Neumer 2005). Everything will stay steady, it is just the idea that will show slight contrast however this can't influence the general significance of the subject and the genuine point by point data that has been offered previously. Part B of the Task This part is about a contextual analysis on Fringe Benefit Tax which is truncated as FBT. A respectability Limited Company by the name Periwinkle is depicted as a bath maker which offer deals on baths legitimately to the general population. On early May, the date being first 2015 to 31st March, the organization being referred to gave a vehicle to one of his workers. The individual who was accommodated the vehicle is one Emma. This arrangement was made to her since she ventures frequently and this was going to offer a help to her (Ordower 2014). The case goes further to make reference to that the recurrence to which Emma utilizes the vehicle isn't constrained and this drives a state of boundless utilization of the vehicle. The vehicle was bought on a similar date that was referenced already and the price tag is evaluated to be $ 33,000. This additionally incorporates the GST esteem. This subsequent part goes further to diagram that for the timespan of first May 2015 to 31st March 2016, Emma had voyage a separation estimation of 10,000 kilometers with the vehicle and have caused all out costs of around $ 550 (Ordower 2013). This complete likewise incorporates the GST simply like the measure of cash that was spent by the legitimacy organization in buying the vehicle. The measure of cash referenced was principally used to provide food for minor fix benefits that have been repaid by the organization. A time of 10 days has additionally been referenced when Emma was interstate and in this manner permitting no utilization of the vehicle around then. Around then, the vehicle was left at the air terminal for yearly fixes and this went on for a multi day time frame (Schwartz 2010). The case goes further to specify that, on first September 2015, Emma was given a credit of $ 500,000 by Periwinkle at a loan cost of about 4.4%. A separate on how the advance was spent was, Emma utilizing $ 450,000 to buy an occasion home and loaning the rest of the sum to her significant other at an intrigue free rate to likewise buy partakes in Telstra (irok and Makov 2007). During that year, there was buy that was made by Emma where she bought bath produced by the organization in conversation at $ 1,300 (Smith 2015). Extra data is that the bath that was offered to Emma typically cost the organization in setting $ 700 to produce and afterward they offer it to the overall population for $ 2,600. Guidance to Periwinkle of its FBT results that are emerging out of the data referenced, covering computations of any FBT obligation for the year finishing 31st March 2016 FBT is a condensing for Fringe Benefit Tax, it is a measure of cash that is paid to a representative however not sorted as either compensation or wages. The FBT enactments give that that, this advantage is just given regard to work. A similar idea is likewise upheld with the talk notes offered in class, as certain parts are in accordance with the inquiry and applies straightforwardly. Much the same as the arrangements of capital increases and capital misfortune, FBT is additionally found in the Income Tax Assessment Act of 1986, and this likewise catches the arrangements of the FBT rate. In thought that when an organization offers a FBT to a worker, it resembles a penance on their part, I would offer the accompanying counsel. The principal counsel that I would offer is on the organization to consider soothing a portion of the advantages offe

15 High-Protein Breakfast Ideas That Will Help You Lose Weight

15 High-Protein Breakfast Ideas That Will Help You Lose Weight If youve been trying to shed some weight but just cant seem to reach your weight loss goals one of the major problems could be your eating habits.It may surprise you to know that by simply eating breakfast and more protein you would see a drastic leap towards your weight loss goals.Whats more, by starting your day with a combination of the two, it pretty much have you as trim and fit as you want in no time.Youre probably thinking how is this possible? Well, studies have shown that consuming 30 grams of protein in your breakfast meal will keep you satisfied and less hungry throughout the day.Take for example a recent survey which showed that people who begin their day consuming between 30 -39 grams of protein, ate 175 fewer calories at lunch.The reason this has a positive effect on your weight loss goals is that foods high in protein take longer to digest, unlike the traditional breakfast foods which are heavily stuffed with carbohydrate.Now, the longer it takes to digest, the lower y our hunger level, and since you won’t get hungry you end up sticking to your healthy eating regime.WHY CHANGE EATING HABITS WHEN I CAN JUST EXERCISE?This may seem like a valid train of thought if you are ignorant of the facts.Research showed how regular exercise is profitable in staying healthy but not as profitable in relation to weight loss. Source: VoxIn the graph above, the study shows that if a hypothetical 200-pound man began 60 minutes of exercise for 4 days every week with the exact same calorie intake for 30 days, it would result in him losing only 5 pounds.In addition to that if the man decided to increase his relax time, as well as food intake even less weight, would be lost.So trying to lose a significant amount of weight by exercising alone is a near impossibility.Now in contrast, in another study on nutrition metabolism, it was seen that people who acquired 30% of their daily calories through protein were able to shed 11 pounds in just 12 weeks. How amazing is that? Source: HealthlineSo, mixing a high-protein breakfast with your routine exercises would boost your weight loss goals as exercise alone wont cut it.However, if youve tried to follow a high -protein diet in the past you’re aware it is a bit difficult to increase your protein intake, especially when youre lacking the right recipes for your breakfast ideas.Thats what this article is for, whether you love it exotic and spicy or sweet and savory, on the way to work or at the breakfast table, there is a meal youll simply adore on this list.1. Mini Egg Frittatas Having just eggs for breakfast may certainly seem plain and boring to you but try these frittatas and they will blow your mind.Mix whole eggs together with extra white eggs and add sautéed vegetables into the mix.If you want some more protein throw in some cheese or turkey sausage.Now, after youve done this pour in this mix into muffin or cupcake tins and let it bake at 350 °F.In order to know when its properly baked, insert a kni fe into it and if the knife comes out clean without stain you can pull it out.Generally, if you use a standard sized muffin tin, it should take anything between 20-25 minutes.Whats really great about this high-protein breakfast is that if you do not like early mornings, you can make them at night and simply reheat it in the morning on your way out.2. Baked Oatmeal with Blueberry-Almond or YogurtEveryone loves oatmeal for breakfast.On its own, its a yummy breakfast stuffed full of whole grains and fiber, but you can increase its all-around nutrition quality by boosting its protein content.By adding chia seeds, almond milk, flax meal, soy milk or even protein powder you can increase your breakfast protein intake with oatmeal.All you need to do is simply stir in flavored or unflavoured protein powder or pour in soy milk right into your oatmeal.Then you can top it with almonds or blueberries for an extra dose of healthy fats, vitamins, and fiber.If you arent a fan of soy milk or protein powder, another option in boosting your oatmeal protein content is to add some cups of Greek yogurt into it.This is quite powerful because it introduces into the oatmeal 11 grams of protein for each serve.Whats more, you can easily carry this breakfast with you, if you have to dash out very early in the morning.In addition to the high protein, you also get filling fiber as well as healthy probiotics.3. Turkish Fried Eggs If you love your breakfast exotic, this is certainly the right meal for you. This modified take on the popular Turkish dish will leave a hard to forget exotic flavor in your mouth.To make this, sauté garlic, red onion, sliced chili pepper and frozen spinach in olive oil. After this is done wait for the veggies to get soft.As soon as the veggies get soft, break in one or two eggs and let it cook together.Then top it with lemon juice, salt, and fatty Greek yogurt.For exotic food lovers, this recipe is a must have, the mixture of the fragrant olive oil, lemon, cream y yogurt, and spicy chili is simply irresistible.4. Cottage Cheese When it relates to boosting your protein intake, many people easily overlook cottage cheese.This low-fat nutritious food is excellent in taste and very easy to make.It is a fantastic addition to your breakfast meals. Whats interesting about low-fat cottage cheese is its protein level, as it is greater than full-fat cheese, even though both of them are fabulous options.If you want to get the best out of it, full up a bowl with low-fat cottage cheese, add some beans and top it with salt, paprika, tomatoes, and pepper.5. Protein Muffins If youve been searching for a portable vegan recipe, protein muffins are the perfect fit.There are numerous ways to get your recommended amount of protein without eating an animal product as a vegetarian and protein muffins are one of them.These muffins are made by using pea protein milk to cook gluten-free oats.As it cooks you add some almond butter, blueberries, flaxseed, and cinnamon. Mix it up till it has a batter-like consistency and you can either eat it right away or bake it for about 20 minutes at 350 °F if you want it a very portable form.6. ShakshukaThis onion, tomato and egg dish is a very popular breakfast food in Israel.As a matter of fact, Shakshuka actually is translated to mean breakfast.To whip this up just cook up red bell peppers, sliced onions, paprika, and tomatoes.Then cook two eggs and once they are boiled, place them on one slice of whole-grain bread.Add the previously cooked red bell peppers, paprika, tomatoes, and sliced onions sauce on the bread as well.Top it off with chili flakes, parsley leaves, pepper and salt for extra flavor.7. Minty Quark Shake In case youve never heard of one a quark is a German-style yogurt, just like a Greek yogurt except it has a cheesecake like the texture and has a lot more protein.Its thick consistency makes it great for whipping up a creamy, decadent protein shake. Keep in mind that protein shakes do not hav e to always be sweet as this has an interesting taste.You can make it by mixing in quark, mint, a pinch of salt, milk, and cucumber.8. Crustless Mini QuichesEggs and vegetables are one of the breakfasts that people enjoy a lot and losing weight doesn’t mean you have to avoid eggs totally; in fact, a perfect mixture of eggs and vegetables in the morning will help you lose some pounds.Eggs and veggies can be combined to give you crustless quiches; all you need to do is to mix fresh eggs with any vegetable like kale, red onion, asparagus or any other vegetable of your choice.Then add seasonings like parsley, cilantro, and garlic, ginger or salt and mix together.After this, bake the mixture in an oven till it is ready and then take it out of the oven.This yummy breakfast will supply your body with lots of nutrients such as vitamin B1, B6, K, A, E, vitamin B12, folate and chromium.If you wish to add a little more protein to the diet, you can make collagen shake.Collagen is pure protein , it doesnt have flavor and it easily dissolves in shakes. You can add blend collagen with berries, nut butter or any other fruit you will like to make you shake with.Collagen aids digestion and also reduces pains in the joint. It strengthens the teeth, hair, and nails and will give you a glowing skin.9. Improved Avocado Toast Avocado toast is one of the most talked about breakfast foods currently and it is excellent for people that want to lose a few pounds because it has a lot of fiber and a healthy dose of fats.However, instead of cooking the conventional Avocado toast, you can amp your own by sprinkling nutritional yeast and adding one or two eggs to the toasted mixture.These two ingredients will add vitamin B and enough protein to the breakfast.If you want to make toast without Avocado, and just want some crunchy toast.All you need to do is to get whole grain bread and spread any nut butter you prefer in the bread, and then you can sprinkle chia seeds on the bread.After you do this, you can eat the toast with any beverage of your choice.This combination is full of lots of fats and healthy fiber and also very rich in protein.10. Protein Pancakes and OatsProtein pancakes are another excellent breakfast menu for shedding some pounds.To make protein pancakes, blend half a cup of egg whites, half a cup of Oatmeal, one cup of cottage cheese and one cup of baking soda. Blend the mixture until it is very smooth.After blending, cook it till it gets done.This pancake contains a high amount of protein which contains the right amount of calories. It will also reduce the risk of having a cardiovascular-related disease.If protein pancakes are too plain for you, you can try something different by making chocolate pomegranate with overnight Oats.You do not have to go through the stress of cooking Oats in the morning; all you need to do is to make the Oats at night.To achieve this, mix Oats with plain Greek yogurt, pomegranate seeds, unsweetened almond milk, chocolate pro tein powder, and chia seeds.This fiber-packed breakfast will delay the digestion process and will give you enough energy to last you a long time. You will stay full for a long time after having this yummy breakfast.11. Omelet and Breakfast WrapsThis list wont be complete without mentioning omelet. Omelet lets you combine meat, cheese, and veggies with eggs.To do something a little extra with your omelet, cook two eggs with cheese, mushrooms, and onions and top it with tomatoes and basil.The many veggies in the omelet are filled with polyphenols; the eggs are packed full with protein while the cheese will give your body calcium.You can also make eggs with lots of greens. Chop spinach, mustard, kale and any other kind of green vegetable. Put the vegetables in a hot pan and stir for about one minute until the vegetable wilts.If you wish to try another source of protein other than eggs, you can make breakfast wrap with smoked salmon. To make breakfast wrap, put smoked salmon on a paleo wrap. Add avocado, roasted vegetables and greens to the wrap.If you wish, you can use whole grain wrap instead of low carb wrap and you can also use chicken or eggs in place of the salmon.You can also use any type of vegetable you like.The breakfast wrap is filled with lots of fiber and fats and it will help you lose lots of weight and also lower the cholesterol level in the body.You can also make breakfast tacos. Add scrambled eggs, avocado slices, lettuce, black beans and Salsa to a taco shell or to a whole grain wrap.This meal is not only portable, but it is also filled with its healthy fats and vitamins and will also help you to lose weight.12. Tofu Scramble If you are tired of eating scrambled eggs, you can try something different by making tofu scramble. All you simply need to do is to replace the eggs with tofu.All you need to do is to mash firm tofu. Pour the mashed tofu into a mixture of salted red bell pepper, onions, garlic or any other type of vegetable you prefer. Cook the mixture on a stove until it is soft.Tofu scramble is rich in protein and is also rich in zinc, calcium, iron, and magnesium. It can be served with potatoes, roti or grain bread or any healthy food you wish to eat it with.Alternatively, you can do something extra by eating your tofu with protein moha.To make protein moha, simply add a scoop or two of protein powder to your cup of coffee. By doing this, you will add a lot of protein into your diet and it is perfect for shedding some pounds.13. Turmeric EggsIf you want to do something different to your scrambled eggs, you can change the spices. Instead of adding cheese, you can add spices like cumin, turmeric or cayenne.Making turmeric scrambled eggs is the same as making your regular scrambled wages its just that instead of adding cheese; you will add turmeric to the mixture.Turmeric scrambled eggs are full of protein and it is great for detoxifying the system.Turmeric manages the blood sugar and also regulates the level of choles terol in the body.Alternatively, if you dont want to make the eggs scrambled, you can have hard-boiled eggs with quinoa. Simply boil eggs and after boiling, let it rest for twelve minutes.After that, eat the hard boiled eggs with cooked quinoa. Hard boiled eggs and quinoa is high in protein.14. Mediterranean/English Muffins and Bread PuddingMediterranean muffins are easy to make and they do not require a lot of ingredients, all you need is canned salmon, feta and eggs.Mix the ingredients and bake in muffin tins, in an oven of about 350 degrees. Leave the mixture to bake in the oven for about twenty to twenty-five minutes.After it is well baked, pull it from the oven and it is ready to eat.You can make lots of these Mediterranean muffins and refrigerate. Then you can microwave every morning when you want to eat it.Even though the Mediterranean muffin may appear plain, it is rich in proteins and healthy fats.Asides Mediterranean muffins, you can also make English muffin. To make an En glish muffin, add a slice of cheese, an egg and two slices of ham or bacon. Wrap in a wax paper and enjoy it.If you think this is boring and you want to do something really fun but nutritional, you can add bread pudding in a mug.To achieve this, mix two tablespoons of vanilla, with one egg, protein powder, two tablespoons of milk and a packet of Stevia. Add two slices of cubed whole grain bread and a chopped apple.Pour the mixture into a mug and put the mug in a microwave, leave it in the microwave for about one minute and bring it out. You can have the pudding with cinnamon and syrup.15. Almond Butter CrackersIf you want to eat some protein but do not have enough time to cook something, you can eat rye crackers and almond butter.The rye cracker and almond butter should be sprinkled with dried fruits and nuts to make it more delicious.You can take this with a warm glass of soy milk.Here is something else you can do with almonds vanilla almond chia pudding.Mix three tablespoons of c hia seed with two tablespoons of almond butter, one cup of unsweetened almond milk, a dash of cinnamon and one teaspoon of vanilla extract.After mixing all these in a jar, put the mixture in the fridge and allow it to stay there overnight.In the morning before eating it, sprinkle some almonds and blueberries on the mixture. The chia seeds in the mixture will give it the texture of a pudding.This breakfast is full of a lot of fiber and protein and it is ideal for people who want to lose weight.CONCLUSIONWeight loss is an extremely tough journey; you need to be extremely dedicated to see significant results.Most times a lot of people embarking on some weight loss goals, downplay the role of their diet and focus on trying to exercise some more.While this is great for your health, exercising without proper eating habits does little to no good. This is why knowing the right type of eating regime to have in relation to your weight loss goals is vital.A high-protein diet is essential if yo u want to see tremendous positive effects concerning weight reduction.However, if youve been confused about what recipes to use to make the most ideal high-protein breakfast, the foods listed in this article will end that confusion!Just pick the best high-protein recipe with regards to your taste and watch those calories fall off.Most of these breakfast recipes are very easy to whip up and can be done in a matter of minutes.If youre an early bird and wont have time to cook in the morning, you can always opt for the recipes which can be made at night and then you reheat them in the morning on your way out.

“Advancing Women in Business Scholarship at NYU Stern

Beginning with the class of 2019, full-time MBA students at NYU Stern will have a new merit-based scholarship opportunity, the Advancing Women in Business Scholarship. The scholarship, which will be awarded to students who demonstrate a deep and enduring commitment to advancing women in business, will cover the first year of tuition and mandatory fees. Stern anticipates awarding $1 million in Advancing Women in Business scholarships to the class of 2019. The scholarship will not be renewable for the second year of MBA studies. The Advancing Women in Business scholarship will be awarded for the first time to students starting the program in fall 2017, with Stern expecting to continue awarding the scholarship in future years as well. There is no special application for the scholarship. As merit-based scholarships, male and female applicants will be awarded The Advancing Women in Business scholarship based on the adcom’s evaluation of the MBA application. Stern Women in Business (SWIB), NYU Stern’s popular and dynamic MBA student club, reinforces the vision behind the scholarship. The club includes four men on its leadership board and creates a supportive community to tackle topics important to women in business and provides opportunities for diverse experiences, perspectives, and resources to be shared. Stern is also a member of The Forte Foundation, a group of top business schools and companies dedicated to directing talented women toward leadership roles in business. The Advancing Women in Business scholarship is funded in part by alumni and members of the Stern School’s Board of Overseers. Learn more by reading the Stern press release here. For tips on getting into NYU Stern, check out Accepted’s NYU Stern B-School Zone.    hbspt.cta.load(58291, '7de5e366-4f37-4aa9-8313-45a286c4665c', {}); For 25 years, Accepted has helped applicants gain acceptance to top undergraduate and graduate programs. Our expert team of admissions consultants features former admissions directors, PhDs, and professional writers who have advised clients to acceptance at top programs worldwide including Harvard, Stanford, Yale, Princeton, Penn, Columbia, Oxford, Cambridge, INSEAD, MIT, Caltech, UC Berkeley, and Northwestern. Want an admissions expert  to help you get Accepted? Click here to get in touch! Related Resources: †¢Ã‚  NYU Stern 2016-17 MBA Essay Tips Deadlines †¢Ã‚  Get an NYU Stern MBA: Interview with Admissions Dean Isser Gallogly †¢Ã‚  MBA Scholarships: How do I Apply and What Should I Emphasize?

The Principles Of Freedom Of An Individual - 934 Words

CHAPTER ONE INTRODUCTION The principle of freedom of an individual is the core tenet of liberalism. The foundation of liberalism is categorized into three. The first is the freedom from arbitrary rule, termed â€Å"negative freedom† which includes freedom of the press, equality before the law, freedom of conscience and right to property. The second set of rights ensures the protection and promotion of the capacity and opportunity for freedom, which is called the â€Å"positive freedom.† Example of such rights are the social and economic rights to health care, education, gainful employment, for human dignity and participation in the society. Thirdly, political rights of democratic representation or participation i.e., right to vote or be voted for to ensure that the other two rights are not infringed on (Kant Political Philosophy, 1993. p. 173). Liberalism today could slightly be different with earlier views as a result of changes in time and history however the fundamental tent of liberty and the ideals of freedom, equality, independence as expressed by Kant remains the same and paramount. Several philosophical views regarding modern political thought on state of nature, social contract and division of powers has immensely been written by both Locke and Kant in their era. REFERENCES CHAPTER TWO MAIN BODY The philosopher emmanuel kant: introduction to profound political thought He was an eighteenth-century philosopher during a period dominated by the ideas of theShow MoreRelatedThe Principles Of Individual Responsibility And Freedom928 Words   |  4 Pagesover the people; telling them that they cannot succeed except under a collective authority instead of being individually motivated and driven to succeed by the principles of life, liberty, and the pursuit of happiness. 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In their specific argumentsRead MoreThe Right Block Free Speech997 Words   |  4 Pagesonly a form individual freedom bu t it is also a form of freedom from a religious doctrine. If these cartoonists were to not express themselves because they fear they are disrespecting other people’s religion, then they themselves are also giving concessions to the principles of that religion. Thus if one views infringement of liberty by the definitions set through the harm and offense principle, it is clear that the interest of a civil society is to protect freedom of speech not to block or regulateRead MorePrivacy And Security : A Technological World1356 Words   |  6 Pagesexactly the balance lay between personal privacy and national security. 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A major debate at the heart of liberalism is how to achieve freedom, positive freedom where the state ‘enables and empowers’ the individual to do more and therefore that individual is more free, or negative freedom where the gov’t should be rolled backRead More John Rawls and Political Liberalism Essay1640 Words   |  7 Pagesjust and stable society of free and equal citizens, who remain profoundly divided by reasonable religious, philosophical, and moral doctrines?† (Rawls 4). More specifically, how do the se concepts help to preserve the traditional liberal values of freedom and equality? And do these concepts help to preserve stability within a pluralistic society? John Rawls book, Political Liberalism, addresses the need for the reformation of the unjust democratic constitutional regime. According toRead MoreThe Battle Of The Confederate Flag1321 Words   |  6 Pagesshall be protected as long as they do not cause reasonable harm to another individual. 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By further analysis of the categorical imperatives and critiques, objections, and the theory’s connections with the â€Å"a priori principles,† Kantian philosophy implication as well as

Marketing Analysis Marketing Mix Essay - 1896 Words

Marketing mix are the set of marketing tools that firm uses to pursue its marketing objectives in the target market. The various variable of the marketing mix : 1. PRODUCT MIX 2. PRICE MIX 3. PLACE MIX 4. PROMOTION MIX Promotion is the important element of marketing mix. Promotion is related with all steps taken to provide information about a product to the customer. It is a common mistake to believe that promotion by business is all about advertising. There are a variety of approaches that a business can take to get their message across to customer althrough advertising is certainly an importanat one. Promotion is all about communication. The main aim of promotion is to ensure that customers are aware of the existence and positioning of products. Promotion is also used to persuade customer that the product is better than competing products and to remind customers about. Increase sales attract new customers, encourage customer loyalty, encourage trial create awareness, inform remind potential customer reassure new customer change attitudes create an image position a product, encourage brand switching to support a distribution channel. The main methods of promotion are : 1. ADVERTISING 2. PUBLIC RELATION AND SPONSORSHIP 3. PERSONAL SELLING 4. DIRECT MARKETING 5. SALES PROMOTION A business will use a range as promotional activities for its product, depending on the marketing strategy and the budget available. The way in which promotion is targeted is split into twoShow MoreRelatedMarketing Mix and Pestle Analysis of Mcdonalds in India3095 Words   |  13 Pagesafter the western operations in India.    The taste of the Chicken burger that one from Bangalore will be similar to that in Delhi if the point of purchase is Mc Donald. 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Views of Voltaire and Molière on the Role of Women in...

The role of women in society has been a controversial one. Most religions see women as being inferior to men and are of the view that women were created as a companion for men. A lot of our social morale stems from religion; hence this help to shape the view that woman is inferior and is to be submissive to their male counterpart. Society has set roles which each sex is expected to play. Gender role is a theoretical construct in the social sciences and humanities that refers to a set of social and behavioral norms that, within a specific culture, are widely considered to be socially appropriate for individuals of a specific sex (Princeston.edu). Women are expected to be docile and agreeable, while men are expected to be head strong and†¦show more content†¦However Armande was of the view that male were not necessary in her life, education was of utmost importance she was appall when her sister (Henriette) told her she wanted to marry Clitandre. Armande stated â€Å"Ah! Heav ens! What a groveling disposition! What a poor part you act in the world, to confine yourself to family affairs, and to think of no more soul-stirring pleasures than those offered by an idol of a husband and by brats of children! Leave these base pleasures to the low and vulgar. Raise your thoughts to more exalted objects; endeavor to cultivate a taste for nobler pursuits; and treating sense and matter with contempt, give yourself, as we do, wholly to the cultivation of your mind.†So Armande general view was that the only way to uplift you was through education. Henriette though she was among learned women she aspired to be nothing like them Moliere also showed a balance with Henriette she was not illiterate but she was not obsessed with being educated. She believed in being a â€Å"traditional women† she was happy with everyday life routine and she didn’t want to ignore the needs of her body, she was fascinated with the idea of being a wife and having children. Henriette stated â€Å"I only have offered to my thoughts a husband, children, and a home; and I see nothing in all this to defile the imagination, or to make one shudder.† Armande can’t understand why her sister rejoices in marrying Clitandre. She thinks sheShow MoreRelatedTo Know About France, and Its History, Culture, French People and Democracy in France5199 Words   |  21 Pagesknow about France and its history, culture, French people and democracy in France ? Introduction France is a powerful democratic country in the world. Every French citizen in France over 18 years old has the right to vote. Freedom of expression is enshrined in law, people are free to gather for any reasons. the French people do strikes very often for their rights and freedom, the strikes in France are common and popular among the world, and French people are free to join any political party

The Family Structure Of The United States - 977 Words

The family structure throughout the last 100 years has changed drastically in the UK. Societies more casual state of mind towards marriage implies it is no longer seen as unusual to be included in a complicated family structure. For instance a Reconstituted family. This is the point at which one or both folks have been married before and had kids and have remarried to shape another family structure also called a step family. Families are no more simply nuclear families. Nuclear family is made up of married folks living with their children. Families now have more muddled structures as compared to the nuclear families. Other family structures include cohabiting parents, lone parent families, homosexual parent families and extended families. The last 100 years have seen changes in legislation, technology, attitudes and expectations and these are all elements that have prompted numerous new trends in the societies like the developing number of new sorts of family structures, more females in exceptionally regarded and paid occupations and an increment in divorce rates. ‘It is realized that 40% of all marriages now end in separation or divorce. There are numerous possible reasons for this pattern which include the (1949) legal aid act and the (1969) divorce law reform act which made separation procedures simpler.’ Another reason could be secularization and the declining disgrace and changing of society mentality towards divorce as more individuals had more adaptableShow MoreRelatedFamily Structure Of The United States848 Words   |  4 PagesDeedocracy: Family Within the summary of our society, Deedocracy takes elements from the U.S.A., and twist them to fix the problems we faced on Earth. 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Grignard Reagent Free Essays

1598 Organometallics 2009, 28, 1598–1605 CoVer Essay The Grignard Reagents Dietmar Seyferth Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 ReceiVed February 4, 2009 During the past 100 years the Grignard reagents probably have been the most widely used organometallic reagents. Most of them are easily prepared in ethereal solution (usually diethyl ether or, since the early 1950s, THF) by the reaction of an organic halide with metallic magnesium (eq 1). Table 1. We will write a custom essay sample on Grignard Reagent or any similar topic only for you Order Now Composition of Diethyl Ether Solutions of Various Grignard Reagents at Equilibrium (in mol %), 2RMgX h R2Mg + MgX2a RX in RX + Mg reacn CH3I C2H5I C2H5Br C2H5Cl n-C3H7I n-C3H7Br n-C3H7Cl C6H5I C6H5Br a RMgX 87. 0 43. 0 41. 0 15. 0 24. 0 24. 0 17. 0 38. 0 30. 0 R2Mg ) MgX2 6. 5 28. 5 29. 5 42. 5 38. 0 38. 0 41. 5 31. 0 35. 0 RX + Mg f RMgX (X ) Cl, Br, I) (1) Most of them are stable in ethereal solution (although atmospheric moisture and oxygen should be excluded) and in general are quite reactive. Discovered by Victor Grignard at the University of Lyon in France in 1900,1 their ease of preparation and their broad applications in organic and organometallic synthesis made these new organomagnesium reagents an instant success. The importance of this contribution to synthetic chemistry was recognized very early, and for his discovery Grignard was awarded a Nobel Prize in Chemistry in 1912. Our cover molecule is the monomeric ethylmagnesium bromide bis(diethyl etherate) (1), whose solid-state molecular structure was determined by an X-ray diffraction study by Lloyd Guggenberger and Robert Rundle in 1964 using crystals isolated from a diethyl ether solution of a C2H5Br/Mg reaction mixture by slow cooling with a stream of cold gaseous nitrogen. 2-4 Adapted from: Schlenk, W. , Jr. Ber. Dtsch. Chem. Ges. 1931, 64, 734. Wilhelm Schlenk and his son discovered 80 years ago, more than one magnesium-containing species exists in the diethyl ether solution of a Grignard reagent. 5 A redistribution of the substituents on magnesium takes place, and the RMgX species ends up in equilibrium with the two symmetrical species, the diorganomagnesium and the magnesium dihalide: the â€Å"Schlenk Equilibrium† (eq 2). 2RMgX h R2Mg + MgX2 (2) Generally written as â€Å"RMgX† in textbooks, monographs and research papers, the Grignard reagents in ethereal solution are more complicated than this simple formula indicates. As (1) (a) Grignard, V. Compt. rend. Hebd. Seances Acad. Sci. 1900, 130, ? 1322. (b) Grignard, V. Dissertation â€Å"Theses sur les combinaisons organo` magnesie nes mixtes et leur application a des syntheses†, University of Lyon, ` ` Lyon, France, 1901. (2) (a) Guggenberger, L. J. ; Rundle, R. E. J. Am. Chem. Soc. 1964, 86, 5344. (b) Guggenberger, L. J. ; Rundle, R. E. J. Am. Chem. Soc. 1968, 90, 5375. 3) A crystalline solid, CH3MgI  · (n-C5H11)2O, was isolated and identi? ed as such by elemental analysis (Mg and I) in 1908: Zerewitinoff, Th. Ber. Dtsch. Chem. Ges. 1908, 41, 2244. The oxonium structure The species that contain Mg-halogen bonds can be precipitated from Grignard reagent solutions in diethyl ether by the addition of 1,4-dioxane. An insoluble, polymeric 1,4-dioxane adduct is formed, leaving behind a solution of R2Mg5sa useful preparation of dialkyl- and diarylmagnesium reagents. 6 Wilhelm Schlenk, Jr. analyzed the 1,4-dioxane precipitations from a number of Grignard reagent solutions. Assuming that the precipitation is essentially instantaneous, i. e. , that the calculated R2Mg, MgX2, and RMgX percentages re? ect the ac tual composition of the Grignard reagent solution at equilibrium, Schlenk reported the compositions collected in Table 1. Direct evidence (5) Schlenk, W. ; Schlenk, W. , Jr. Ber. Dtsch. Chem. Ges. 1929, 62, 920. (6) (a) Cope, A. C. J. Am. Chem. Soc. 1935, 57, 2238. (b) As Erwin Weiss found, evaporation of diethyl ether solutions of methyl- and ethylmagnesium bromide and chloride at reduced pressure followed by heating of the colorless solid residues at ca. 00  °C and 0. 001 mmHg for several hours gave a mixture of the respective pure, solvent-free, polymeric R2Mg compounds and magnesium halides. The solid MgCl2 thus obtained differed from a sample obtained from a MgCl2 melt in that its lattice showed a strong stacking disorder. This form of MgCl2 had an extremely high surface area: Weiss, E. Chem. Ber. 1965, 98, 2805. (7) Schlenk, W. , Jr. Ber. Dtsch. Chem. Ges. 1931, 64, 734 Further additions to the examples in Table 1 were soon thereafter reported by other workers: (a) Noller, C . R. ; Hilmer, F. B. J. Am. Chem. Soc. 1932, 54, 2503. (b) Johnson, G. O. Adkins, H. J. Am. Chem. Soc. 1932, 54, 1943. (c) Cope, A. C. J. Am. Chem. Soc. 1934, 56, 1578. was written for this compound. Earlier workers had isolated noncrystalline solid samples of etherates, e. g. , C2H5MgI  · (C2H5)2O and RMgI  · 2(C2H5)2O. (4) Other early Grignard reagent crystal structures: (a) Stucky, G. D. ; Rundle, R. E. J. Am. Chem. Soc. 1964, 86, 4825 (C6H5MgBr  · 2Et2O). (b) Vallino, M. J. Organomet. Chem. 1969, 20, 1 (CH3MgBr  · 3THF). . 10. 1021/om900088z CCC: $40. 75 ? 2009 American Chemical Society Publication on Web 03/16/2009 Organometallics, Vol. 28, No. 6, 2009 1599 Figure 1. Association of several Grignard compounds in tetrahydrofuran (J. Am. Chem. Soc. 1969, 91, 3847. ). that solutions of â€Å"CH3MgBr† in diethyl ether contain CH3MgBr and (CH3)2Mg was obtained by Ashby and co-workers by means of 1H NMR spectroscopic measurements at -105  °C. Solutions of â€Å"t-butylmagnesium chloride† in diethyl ether also were studied. 8 The tendency of the halide substituents in the RMgX and MgX2 species present in ethereal solution at equilibrium to form bridges between magnesium atoms, Mg-X-Mg, in a Lewis base/Lewis acid type interaction further complicates the nature of the Grignard reagent in ethereal solvents. In a very thorough study of the association factors of various Grignard reagents in diethyl ether and THF by careful ebullioscopic molecular weight measurements, Eugene Ashby and Frank Walker at the Georgia Institute of Technology found that monomeric, dimeric, and higher oligomeric species were present, depending on the solvent and the halogen and the organic substituents on the magnesium atom. 9 Included in this study along with data for the â€Å"RMgX† solutions were data for a few R2Mg compounds and for the magnesium dihalides. As Figure 1 shows, the observed association factor (the i value is the apparent molecular weight divided by the formula weight of the monoetherate) shows that the Grignard reagents and (C6H5)2Mg are close to monomeric in the relatively strong Lewis basic THF. The picture is quite different in diethyl ether solution (Figures 2 and 3), with association factors of 1 to nearly 4 for solute concentrations up to ca. 3 molal. It is not clear what these i values mean in terms of the actual species present in these solutions. On the assumption that the Schlenk equilibrium is operative in all cases, in view of the presence of a signi? cant concentration of MgX2, one cannot expect only simple solvated species of type i(R)Mg-X] n [ i (average n ) i). Toney and Stucky isolated crystals of a dimeric species, 2, from a solution of â€Å"C2H5MgBr† in di-n-butyl ether by addition of this solution to triethylamine. 10 The molecular Figure 2. Association of alkylmagnesium chlorides in diethyl ether. Demonstration of importance of halogen vs R group in determining the form of association in diethyl ether (J. Am. Chem. Soc. 1969, 91, 3848. ). Figure 3. Association of several alkyl- and arylmagnesium bromides and iodides and related magnesium compounds in diethyl ether (J. Am. Chem. Soc. 1969, 91, 3848. ). structure, as determined by X-ray analysis, contained a double Br bridge with the ethyl groups in a trans arrangement. That (8) In â€Å"CH3MgBr† solutions in diethyl ether: (a) Ashby, E. C. ; Parrish, G. ; Walker, F. Chem. Commun. 1969, 1464. (b) â€Å"(CH3)3CMgCl† solutions in diethyl ether at-26  °C: Parris, G. ; Ashby, E. C. J. Am. Chem. Soc. 1971, 93, 1206. (9) (a) Walker, F. W. ; Ashby, E. C. J. Am. Chem. Soc. 1969, 91, 3845. (b) Ashby, E. C. Bull. Soc. Chim. Fr. 1972, 2133 (review, in English). (c) Meisenheimer, J. ; Schlichenmaier. Ber. Dtsch. Chem. Ges. 1928, 61 (an earlier, similar, but more limited study in diethyl ether). more complicated structures can be present in an â€Å"RMgX† solution in diethyl ether was demonstrated by the determination of the X-ray crystal structure of a crystalline compound obtained from a THF solution of â€Å"C2H5MgCl† of composition C2H5Mg2Cl3. This compound was not a simple Cl-bridged dimer, as the empirical formula might suggest. Actually, it was a tetramer (Figure 4) in which the Mg atoms have a coordination number greater than 4. 1 There is a caveat, however: the species that crystallizes from a Grignard reagent solution does not necessarily directly re? ect what species are swimming around in the solution. The crystalline solid shown in Figure 4 could well have self-assembled during the crystallization process by combination of two molecules of the C2H5Mg2Cl3 dimer and not been present in solution at all. Even in the case of monomeric â€Å"RMgX† in THF solution, the Schlenk equilibrium will be operative and the strongly Lewis basic THF apparently prevents halide bridging between Mg atoms. Consequently, the (10) Toney, J. ; Stucky, G. D. Chem. Commun. 1967, 1168. (11) Toney, J. ; Stucky, G. D. J. Organomet. Chem. 1971, 28, 5. 1600 Organometallics, Vol. 28, No. 6, 2009 Scheme 1 Figure 4. Molecular structure of [C2H5Mg2Cl3(C4H8O)3]2, a tetrameric Grignard reagent. Modi? ed from Toney and Stucky (J. Organomet. Chem. 1971, 28, 15. (copyright 1971, with permission from Elsevier)). presence of monomeric RMgX, R2Mg, and MgX2, all solvated, would result in the measurement of an association factor of 1, as Walker and Ashby observed. There are so many factors that bear on the question of the constitution of a given Grignard reagent in ethereal solutionsthe Lewis basicity and steric properties of the ether solvent, the electronegativity and size of the halogen atom in RMgX, the nature and steric properties of the organic substituent on the magnesium atom. These will affect the magnitude of the equilibrium constant of the Schlenk equilibrium and the extent of Mg-X-Mg bridging. For most applications in synthetic chemistry it will suf? ce to take the easy way outsto regard and to write the Grignard reagent as RMgX. There is another interesting and useful property of ethereal Grignard reagent solutions. The magnesium species are weak electrolytes in such solvents of low dielectric constant, and â€Å"RMgX† solutions conduct an electric current. 12 The electrolysis of solutions of organomagnesium halides was studied in some detail by Kondyrew at the State Research Institute in Leningrad13 and by Ward Evans and his students at Northwestern University. 14 During the electrolysis, magnesium species migrate both to the cathode and to the anode. Scheme 1 shows the simplest picture based on RMgX. Metallic magnesium is formed at the cathode. 12) The earliest report appears to be a 1912 French paper: Jolibois, P. Compt. rend. Hebd. Seances Acad. Sci. 1912, 155, 213. See also: Nelson, ? J. M. ; Evans, W. V. J. Am. Chem. Soc. 1917, 39, 82. (13) (a) Kondyrew, N. W. Ber. Dtsch. Chem. Ges. 1925, 58, 459. (b) Kondyrew, N. W. ; Manojew, D. P. Ber. Dtsch. Chem. Ges. 1925, 58, 464. (c) Kondyrew, N. W. Ber. Dtsch. Chem. Ges. 1928, 61, 208. (d) Kondyrew, N. W. ; Ssusi, A. K. Ber. Dtsch. Chem. Ges. 1929, 62, 1856. (14) The Evans group published many papers in J. Am. Chem. Soc. during the 1933-1942 period. See, for example: (a) Evans, W. V. ; Lee, F. H. J. Am. Chem. Soc. 1934, 56, 654. (b) Evans, W. V. ; Field, E. J. Am. Chem. Soc. 1936, 58, 720. (c) Evans, W. V. ; Braithwaite, D. J. Am. Chem. Soc. 1939, 61, 898. (d) Evans, W. V. ; Braithwaite, D. ; Field, E. J. Am. Chem. Soc. 1940, 62, 534. (e) Evans, W. V. ; Pearson, R. J. Am. Chem. Soc. 1942, 64, 2865. The alkyl radicals formed at the anode can undergo the usual alkyl radical processes of coupling (to R-R), disproportionation (to RH + R(-H)), or, if the anode is composed of a reactive metal such as zinc, aluminum, cadmium, or lead, they can attack the anode to form an organometallic compound. A graduate student of Evans, David G. Braithwaite, joined the Nalco Chemical Co. after he graduated and developed an electrolytic process for the commercialscale syntheses of tetramethyl- and tetraethyllead antiknock agents in which the respective alkyl Grignard reagents were electrolyzed in a mixed THF/diethylene glycol dimethyl ether solvent system using a lead anode and a steel cathode. 15 The reactions of the Grignard reagents with organic, organometallic, and inorganic substrates and their applications are too numerous and varied to be covered here. Not only do they ? nd extensive use on a small to moderate scale in research laboratories but they also have been prepared and utilized on a large scale in diverse industrial processes. For the most part they react as nucleophilic reagents, as would be expected, on the basis of the polarity of the carbon-magnesium bond, C? –Mg? +. However, they also can undergo electron transfer reactions with appropriate electron-acceptor substrates. They are weak bases capable of deprotonating the stronger weak organic acids such as terminal acetylenes and cyclopentadiene. Their basicity can be enhanced (as can be the basicity of organolithium reagents) by the addition to RMgX solutions in ethers of additives such as hexamethylphosphoric triamide (HMPA) and N-methyl-2-pyrrolidinone (NMP) or alkali-metal alkoxides. All such information can be found in books devoted solely or in part to Grignard reagents. 16 Two special topics are of current interest and merit special mention. (1) The preparation of highly functionalized organomagnesium reagents by Paul Knochel and his co-workers at the University of Munich17 by means of halogen-magnesium exchange (e. . , eq 3). The availability of reagents such as 3-8 (which must be utilized at low temperature) has added a new and spectacular dimension to Grignard reagent chemistry. (2) The synthesis of ole? ns, styrenes, 1,3-dienes and biaryl derivatives by the crosscoupling of Grignard reagents with organic halides. The crosscoupling of Grignard reagents with vinylic halides was discovered by Morris Kharasch and Charl es Fuchs at the University of Chicago Organometallics, Vol. 28, No. 6, 2009 1601 Table 2. Transition Metal Halide Catalyzed Homocoupling of Phenylmagnesium Iodidea metal halide FeCl2 CoBr2 NiBr2 RuCl3 RhCl3 PdCl2 OsCl3 IrCl3 a amt, mol 0. 01 0. 01 0. 03 0. 0036 0. 0036 0. 00566 0. 00275 0. 003 amt of C6H5MgI, mol 0. 03 0. 03 0. 095 0. 0108 0. 013 0. 0163 0. 007 0. 01 yield of biphenyl, % 98 98 100 99 97. 5 98 53 28 Taken from: J. Am. Chem. Soc. 1939, 61, 957. in 1943 during the classic studies of Kharasch on the chemistry of Grignard reagents in the presence of transition-metal halides. 6b Kharasch and Fuchs found that arylmagnesium bromides in diethyl ether reacted readily with vinylic halides of type RCHdCHX and R2CdCHX (but not CH2dC(R)X) to give styrenes in 50-75% yield when the reactions were carried out in the presence of 5 mol % of CoCl2 (eq 4). 18It was reported that other metal halides (of iron, nickel, and chromium) also were effective catalysts of this cross-coupling reaction. Benzylmagnesium chloride also reacted in this manner with vinyl bromide to give PhCH2 CHdCH2 in 75% yield. Alkylmagnesium halides such as cyclohexyl- and n-butylmagnesium bromide, on the other hand, gave only â€Å"small to negligible† yields of the expected coupling product. The ArMgBrderived biaryl usually was obtained as a byproduct in these reactions. Such homocoupling of arylmagnesium halides in the presence of a transition metal halide as well as copper and silver halides was a known reaction. It had been investigated in 1939 by Gilman and Lichtenwalter, who found that aryl Grignard reagents undergo homocoupling in the presence of ca. 0 mol % of various transition-metal halides in diethyl ether solution to give the respective biaryl in high yield in most cases (eq 5, Table 2). 19 The metal halide, in addition to being the needed catalyst precursor, also served as an oxidizing agent and, in some cases (CoBr2, NiCl2, RhCl3), formation of a black solid indicated complete reduction to the metal. not occur in the absence of the organic halide but in its presence was vigorously exo thermic. The added organic halide was only partially consumed and did not show up in the biaryl product. When p-bromotoluene was added to a phenylmagnesium bromide/CoCl2 catalyst reaction mixture, only biphenyl was formed. A remarkable reaction! smost likely a free radical process, as Kharasch suggested. The organic halide was believed to function as an oxidizing agent. This interesting, simple, and potentially useful cross-coupling reaction, as exempli? ed in eq 4, was not adopted by the synthetic organic community right away. After a long dormancy it was rediscovered some 30 years later by a number of groups in the USA, Japan, and France, all of whom apparently were not aware of the 1943 Kharasch/Fuchs JACS paper. 1 Transition-metal catalysts other than CoCl2 were used, but the concept and the basic reaction were the same. In 1971 Tamura and Kochi reported a thorough study of the cross-coupling of Grignard reagents with vinylic halides catalyzed by soluble iron species in concentrations of ca. 10-4 M in THF at 0-25  °C. 26,27 Various Fe(III) compounds could be used as Fe catalyst pr ecursors; the best were Fe(III) -diketonates such as Fe(RC(O)CHC(O)R)3 (R ) Ph, CH3, t-Bu). These exothermic reactions were not free radical processes. The reactions of cis- and trans-propenyl bromide proceeded with retention of geometric con? uration (eqs 6 and 7) and were not adversely affected by the presence of 0. 4 M styrene. A ArMgBr + RCHdCHX 9 ArCHdCHR + MgBrX 8 (X ) Cl, Br) CoCl2 5 mol % (4) 2ArMgX + MXn f Ar-Ar + MgX2 + MXn-2 (5) A novel catalytic process for such ArMgX to Ar-Ar coupling was discovered by Kharasch and Fields when ethereal solutions of an aryl Grignard reagent that contained a catalytic amount (3 mol %) of CoCl2 were heated at re? ux for 1 h and then treated with an equivalent amount of an organic halide (C6H5Br, C2H5Br, i-C3H7Cl). 20 The coupling reaction to give Ar-Ar did (15) (a) Bott, L. L. Hydrocarbon Process. Petrol. Re? ner 1965, 44, 115. (b) Guccione, E. Chem. Eng. 1965, (June 21), 102. See also Part 2 of the tetraethyllead essay: (c) Seyferth, D. Organometallics 2003, 22, 5154 (pages 5172-5174). (16) (a) Krause, E. ; von Grosse, A. Die Chemie der metall-organischen Verbindungen; Gebruder Borntrager: Berlin, 1937; pp 14-61, 110-114. ? ? (b) Kharasch, M. S. ; Reinmuth, O. Grignard Reactions of Nonmetallic Substances; Prentice Hall: New York, 1954. (c) Handbook of Grignard Reagents; Silverman, G. S. , Rakita, P. E. , Eds. ; Dekker: New York, 1996. d) Grignard Reagents-New DeVelopments; Richey, H. G. , Ed. ; Wiley: Chichester, New York, 2000. (e) The Chemistry of Organomagnesium Compounds; Rappaport, Z. , Marek, L. , Eds. ; Wiley-VCH: Weinheim, Germany, 2008. (17) Knochel, P. ; Dohle, W. ; Gommermann, N. ; Kneisel, F. F. ; Kopp, F. ; Korn, T. ; Sapountzis, J. ; Vu, V. A. Angew. Chem. , Int. Ed. 2003, 42, 4302 (review). (18) Kharasch, M. S. ; Fuchs, C. F. J. Am. Chem . Soc. 1943, 65, 504. (19) Gilman, H. ; Lichtenwalter, M. J. Am. Chem. Soc. 1939, 61, 957. and earlier (back to 1914) references cited therein. 20) Kharasch, M. S. ; Fields, E. K. J. Am. Chem. Soc. 1941, 63, 2316. mechanism involving an organoiron(I) intermediate, obtained by reduction of the Fe(III) precursor by the Grignard reagent, was suggested. The results of a few experiments carried out on a 30-40 mmol scale (Table 3) showed that such iron-catalyzed reactions would be useful in the synthesis of ole? ns, but a broader study to optimize them and to broaden the scope of their application was not undertaken. The coupling of vinylic Grignard reagents with alkyl halides is catalyzed also by Ag(I) salts. 8 Thus, cis-propenylmagnesium (21) Two later â€Å"historical notes†22,23 and two book chapters24,25 that dealt with the cross-coupling reactions of Grignard reagents with vinylic halides also did not cite the Kharasch/Fuchs paper. (22) Tamao, K. J. Organomet. Chem. 2002, 653 , 27. (23) Murahashi, S. -I. J. Organomet. Chem. 2002, 653, 27. (24) Kochi, J. K. Organometallic Mechanisms and Catalysis; Academic Press: New York, 1978; Chapter 14, Sections III and IV. (25) Hou, S. ; Negishi, E. -i. In Handbook of Organopalladium Chemistry; Negishi, E. -i. , Ed. , Wiley: New York, 2002; Vol. 1,Chapter III. 2. 6, pp 335408. As a historical note, the following quotation from this reference (p 335) is of interest: â€Å"Although the reaction of Grignard reagents with organic halides was shown to be catalyzed by various late transition metal compounds (the Kharasch reaction) in the 1950s, it was not until the early 1970s that the applicability of this catalytic method was extended to the cross-coupling involving alkenyl and aryl halides catalyzed by Ag, Fe and other late transition metals. † (26) (a) Kochi, J. ; Tamura, M. J. Am. Chem. Soc. 1971, 93, 1487. (b) Tamura, M. ; Kochi, J. Synthesis, 1971, 303. (27) Full papers: (a) Neumann, S. M. ; Kochi, J. K. J. Org. Chem. 1975, 40, 599. (b) Smith, R. S. ; Kochi, J. K. J. Org. Chem. 1976, 41, 502. (c) Reviews: ref 24. (d) Kochi, J. K. J. Organomet. Chem. 2002, 653, 11 (historical note). (28) (a) Whitesides, G. M. ; Casey, C. P. J. Am. Chem. Soc. 1966, 88, 4541. (b) Tamura, M. ; Kochi, J. J. Am. Chem. Soc. 1971, 93, 1483. 1602 Organometallics, Vol. 28, No. 6, 2009 Table 3. Alkenylation of Grignard Reagents using FeCl3 as Precatalyst (in THF)a R MgBr (amt, mmol) n-C6H13MgBr (40) CH2dCH(CH2)4MgBr (36) n-C6H13MgBr (40) a 1 R2Br (amt, mmol) CH2dCHBr (204) CH2dCHBr (102) CH3CHdCHBr (355) FeCl3 (amt, mmol) 0. 05 0. 05 0. 10 reacn temp,  °C 0 25 25 product (yield, %) n-C6H13CHdCH2 (83) CH2dCH(CH2)4CHdCH2 (64) n-C6H13CHdCHCH3 (67) (53/47 cis/trans mixture) Taken from: Synthesis 1971, 6, 303. Scheme 2 bromide reacted with methyl bromide in THF in the presence of an Ag(I) catalyst to give cis-butene-2, but a similar reaction of trans-propenylmagnesium bromide gave a 7:3 mixture of cisand trans-butene-2, respectively. 28b Apparently propenyl radicals were involved. A similar Grignard reagent based cross-coupling, ole? n synthesis in which a copper(I) catalyst was used was published by French workers. 9 Normant et al. reported that their reactions (e. g. , n-Bu(Et)CdCHI + i-PrMgCl in THF at -20  °C with a Cu(I) catalyst) proceeded with retention of con? guration. 29a For a reaction of CH3CHdC(CH3)MgCl with n-C3H7I in THF at 0  °C using CuI as catalyst, Linstrumelle reported that the coupling product obtained in 97% yield was 88% cis and 12% trans, while a similar reac tion of CH2dC(CH3)MgBr with trans-n-C6H13CHdCHI gave a 4:1 trans/cis product. 29b TheuseofNi(II)catalystprecursorsforGrignardreagent-vinylic halide cross-coupling was reported in 1972 by Corriu and Masse30 and by Tamao, Sumitani, and Kumada. 1 The French group found Ni(II) acetylacetonate to be the most effective catalyst precursor, while the Japanese group favored a bis(tertiary phosphine)NiCl2 catalyst precursor and, especially, chelating diphosphine complexes such as (Ph2PCH2CH2PPh2)NiCl2. Reactions carried out in diethyl ether at re? ux generally gave excellent yields. This procedure has been carried out commercially on an industrial scale in the preparation of p-chloroand p-tert-butylstyrene. 32 Finally, the last to be discovered at that time and the most versatile procedure for the cross-coupling of Grignard reagents (29) (a) Normant, J. F. Commercon, A. ; Cahiez, G. ; Villieras, J. Compt. ? rend. Hebd. Seances Acad. Sci. , Ser. C 1974, 278, 967. (b) Derguini? Boumechal, F. ; Linstrumelle, G. Tetrahedron Lett. 1976, 3225. (30) Corriu, R. J. P. ; Masse, J. P. J. Chem. Soc. , Chem. Commun. 1972, 144. (31) (a) Tamao, K. ; Sumitani, K. ; Kumada, M. J. Am. Chem. Soc. 1972, 94, 1375. (b) See also ref 22. Later work: (c) Tamao, K. ; Kiso, Y. ; Sumitani, K. ; Kumada, M. J. Am. Chem. Soc. 1972, 94, 9268. (d) Kiso, Y. ; Tamao, K. ; Kumada, M. J. Organomet. Chem. 1973, 50, C12. (e) Kiso, Y. ; Tamao, K. ; Miyake, N. ; Yamamoto, K. ; Kumada, M. Tetrahedron Lett. 974, (No. 1), 3. (f) Tamao, K. ; Sumitani, K. ; Kiso, Y. ; Zembayashi, M. ; Fujioka, A. ; Kodama, S. ; Nakajima, I. ; Minato, A. ; Kumada, M. Bull. Chem. Soc. Jpn. 1976, 49, 1958. (g) Tamao, K. ; Kodama, S. ; Nakajima, I. ; Kumada, M. ; Minato, A. ; Suzuki, K. Tetrahedron 1982, 38, 3347. (32) Banno, T. ; Hayakawa; Umeno, M. J. Organomet. Chem. 2002, 653, 288. (33) (a) Yamamura, M. ; Moritani, I. ; Murahashi, S. -I. J. Organomet. Chem. 1975, 91, C39. Full paper: (b) Murahashi, S. -I. ; Yamamura, M. ; Yanagisaw a, K. -i. ; Mita, N. ; Kondo, K. J. Org. Chem. 1979, 44, 2408. (c) Historical note: ref 23. ith vinylic and aryl halides, that catalyzed by palladium complexes, was reported by Shun-Ichi Murahashi and coworkers in 1975. 33a The reactions were carried out in diethyl ether/benzene at room temperature using (Ph3P)4Pd as the catalyst precursor, and they proceeded stereospeci? cally in excellent yield (Scheme 2). Dang and Linstrumelle also used this procedure to prepare 1,3-dienes stereospeci? cally by the reaction of vinylic iodides with vinylic Grignard reagents. 34 Palladium-catalyzed cross-coupling of Grignard reagents with organic halides has been a very active area in organic synthesis. Reference 25 reviews (up to 2002) its application in (alkenyl) MgX-ArX, ArMgX-(alkenyl)X, and (alkenyl)MgX-(alkenyl)X coupling processes. A further chapter in this book deals with ArMgX-Ar? X coupling. 35 Another surge of research activity on cross-coupling of Grignard reagents with organic halides started around the turn of the century and still appears to be in progress at the present time (January 2009). Interest has revived in the use of iron complexes as precatalysts for the cross- and homocoupling of Grignard reagents,36 since iron complexes are cheaper than those of palladium and are nontoxic. The iron-catalyzed cross-coupling of organomagnesium bromides with vinylic bromides, although it produced ole? ns in good yield, was of interest to Jay Kochi, as noted above, primarily from the point of view of its reaction mechanism rather than of its potential for application in organic synthesis. After some 25 years several research groups carried out much experimental work which has shown iron-catalyzed cross-coupling and homocoupling of Grignard reagents to be broadly applicable and very useful additions to the methods of organic synthesis. In 1995 Gerard Cahiez, at the Universite Pierre et Marie Curie ? ? in Paris, during the course of his extensive investigations of organomanganese chemistry, found that the cross-coupling of vinylic bromides with alkyl, vinylic, and phenylmanganese chlorides could be effected in good yield in the presence of 3 mol % of iron(III) acetylacetonate in a THF/N-methyl-2pyrrolidinone (NMP) mixed solvent at room temperature. 37 In a thorough study, this reaction was extended to the crosscoupling of vinylic halides with alkylmagnesium halides using 1 mol % of Fe(acac)3 and the same solvent mixture. 8 High yields of ole? nic products were obtained. Successful crosscoupling of Grignard reagents with AcO(CH2)6CHdCHCl, CH3C(O)(CH2)3CHdCHCl, Cl(CH2)4CBrdCH2, 9, and 10 are noteworthy as examples of the selectivity and functional group tolerance of this reaction. The scope of this chemistry was extended further when some of Knochel’s functionally substituted aryl Grignard reagents17 (vide supr a) were reacted with vinylic bromides and iodides. 39 The cross-coupling reaction between aryl Grignard reagents and vinylic bromides and iodides also was found by Cahiez and co-workers to give ole? ic products in good yield with Organometallics, Vol. 28, No. 6, 2009 1603 Table 4. Iron-Catalyzed Biaryl Coupling Reactions a Table 5. Iron-Catalyzed Homocoupling of Grignard Reagents with Atmospheric Oxygen as Oxidanta a Taken from: J. Am. Chem. Soc. 2007, 129, 13788. palladium or nickel precatalysts. 42 Of these procedures, that of Cahiez et al. 41f appears to be the most useful. Alkyl halide/ alkylmagnesium halide cross-coupling is not a practical process. 43 RMgX + R? X 9 R-R? + MgX2 8 [Fe] (8) Iron-catalyzed reactions of aryl Grignard reagents with aryl halides to give biaryls generally are not synthetically useful. The desired cross-coupling products are obtained in only poor yield, the main product being the homocoupled biaryl derived from the aryl Grignard reagent (eq 9) (recall the Gilman/ Lichtenwalter and Kharasch/Fields reactions, vide supra). ArMgX + Ar? X f Ar-Ar? + (low yield) (major Ar-Ar product) (9) a Taken from: J. Am. Chem. Soc. 2007, 129, 9844. retention of geometric con? guration when carried out in THF solution in the presence of 10 mol % of MnCl2. 0 As noted above, Kharasch and Fuchs had found that attempts to cross-couple aryl Grignard reagents with alkyl halides in the presence of catalytic amounts of CoCl2 were unsuccessful. On the other hand, such reactions do occur in the presence of an iron precatalyst and various additives (eq 8, R? ) alkyl), as summarized in ref 36. A number of other groups have reported the results of their research directed tow ard development of an effective procedure for the process shown in eq 8, all using an iron precatalyst of one kind or another, various additives such as TMEDA, NMP, etc. nd generally diethyl ether (but sometimes THF) as solvent. 41 It is noteworthy that primary and secondary alkyl halides, i. e. , ones that contain hydrogen substituents on the carbon atom, can be cross-coupled with aryl Grignard reagents, a process that cannot be realized using (34) Dang, H. P. ; Linstrumelle, G. Tetrahedron Lett. 1978, 191. (35) Anastasia, L. ; Negishi, E. -i. Chapter II. 2. 5, pp 311-344, in ref 25. (To date palladium and nickel catalysts have been widely used to effect aryl-aryl cross-coupling reactions. However, arylmagnesium halides were found to undergo cross-coupling with aryl halides that contain electron-withdrawing activating substituents ortho or para with respect to the halogen substituent in the presence of 10 mol % of manganese(II) chloride (eq 10). 44 Cyclohexyl and 2-methylpropenyl G rignard reagents reacted with such substituted halobenzenes in a similar manner. Very (36) (a) Cahiez, G. ; Duplais, C. â€Å"Iron-Catalyzed Reactions of Grignard Reagents†, Chapter 13, pp 594-630 in ref 16e. (b) Furstner, A. ; Leitner, ? A. ; Mendez, M. ; Kraus, H. J. Am. Chem. Soc. 2002, 124, 13856 (a long ? paper that brings an excellent discussion of the literature, of questions concerning mechanism, and original results). (c) Sherry, B. D. ; Furstner, ? A. Acc. Chem. Res. 2008, 41, 1500. (37) Cahiez, G. ; Marquis, S. Tetrahedron Lett. 1996, 37, 1773. (38) Cahiez, G. ; Avedissian, H. Synthesis 1998, 1199. (39) Dohle, W. ; Kopp, F. ; Cahiez, G. ; Knochel, P. Synlett 2001, 1901. 1604 Organometallics, Vol. 28, No. 6, 2009 Table 6. Manganese-Catalyzed Homocoupling of Grignard Reagents with Atmospheric Oxygen as Oxidanta Scheme 4 THF to a mixture of 3 mol % of FeF3  · 3H2O and 9 mol % of an N-heterocyclic carbene (SIPr  · HCl). In one example, chlorobenzene (1. 0 equiv) and p-CH3C6H4MgBr (1. 2 equiv) were added to this catalyst system and the reaction mixture was stirred at 60  °C for 1 day. The desired product, p-CH3C6H4-C6H5, was obtained in 98% yield. The homocoupling product, biphenyl, was present only in trace amount, while CH3C6H4C6H4CH3 was formed in 3% yield. Some examples of the application of this remarkable reaction are shown in Table 4. Good results were obtained only with aryl chlorides. Aryl bromides and iodides gave low biaryl yields. A German group reported similar MnCl2-catalyzed cross-coupling between various heterocyclic chlorides and aryl as well as alkyl Grignard reagents: e. g. , eq 11. 46 a Taken from: J. Am. Chem. Soc. 2007, 129, 13788. The homocoupling reaction of aryl Grignard reagents, mentioned earlier, also has received renewed attention recently, and synthetically useful procedures have resulted. Nagano and Hayashi developed a procedure in which the reaction is carried out in re? uxing diethyl ether in the presence of 1-5 mol % of FeCl3, NMP and 1. molar equiv of 1,2-dichloroethane (which serves as the oxidant). 47 Cahiez and co-workers have improved this procedure by using THF as solvent, in which arylmagnesium halides, including the chlorides, are more easily prepared. 48 This procedure works well with Knochel’s functional arylmagnesium halides (Scheme 3). Of interest also is the clever construction of the tricyclic system 11 by intramolecul ar homocoupling (Scheme 4). (40) (a) Cahiez, G. ; Gager, O. ; Lecomte, F. Org. Lett. 2008, 10, 5255. (b) Alami, M. ; Ramiandrasoa, P. ; Cahiez, G. Synlett 1998, 325. 41) A selection: (a) Martin, R. ; Furstner, A. Angew. Chem. , Int. Ed. ? 2004, 43, 3955 (see also ref 36b and references cited therein). (b) Nagano, T. ; Hayashi, T. Org. Lett. 2004, 6, 1297. (c) Bedford, R. B. ; Bruce, D. W. ; Frost, R. M. ; Goodby, J. W. ; Hird, M. Chem. Commun. 2004, 2822. (d) Nakamura, N. ; Matsuo, K. ; Ito, S. ; Nakamura, E. J. Am. Chem. Soc. 2004, 126, 3686. (e) Bedford, R. B. ; Bruce, D. W. ; Frost, R. M. ; Hird, M. Chem. Commun. 2005, 4161. (f) Cahiez, G. ; Habiak, V. ; Duplais, C. ; Moyeux, A. Angew. Chem. , Int. Ed. 2007, 46, 4364. g) Cahiez, G. ; Duplais, C. ; Moyeux, A. Org. Lett. 2007, 9, 3253. (h) Guerinot, A. ; Reymond, S. ; Cossy, J. Angew. ? Chem. , Int. Ed. 2007, 46, 6521. (42) However, Terao and Kambe have recently developed new Pd- and Ni-based precatalyst systems which avoid the pro blem of -elimination of primary and secondary alkyl groups: Terao, J. ; Kambe, M. Acc. Chem. Res. 2008, 41, 1545. (43) (a) Tamura, M. ; Kochi, J. J. Organomet. Chem. 1971, 31, 289. (b) Rollick, K. L. ; Nugent, W. A. ; Kochi, J. K. J. Organomet. Chem. 1982, 225, 279. (44) Cahiez, G. ; Lepifre, F. Ramiandrasoa, P. Synthesis 1999, 2138. (45) Hatakeyama, T. ; Nakamura, M. J. Am. Chem. Soc. 2007, 129, 9844. (46) Rueping, M. ; Ieawsuwan, W. Synlett 2007, 247. (47) Nagano, T. ; Hiyama, T. Org. Lett. 2005, 7, 491. (48) Cahiez, G. ; Chaboche, C. ; Mahuteau-Betzer, F. Org. Lett. 2005, 7, 1943. Scheme 3 special, but generally applicable, reaction conditions developed by Japanese workers45 have ? nally provided the possibility of clean aryl-aryl cross-coupling reactions in which competitive homocoupling of the aryl Grignard reagent has been almost completely suppressed. In this procedure an active catalyst system was prepared by addition of 18 mol % of C2H5MgBr in Organometallics, Vol. 28, No. 6, 2009 1605 A further improvement resulted when it was found that atmospheric oxygen could replace the 1,2-dihaloethane as oxidant in the homocoupling of aryl, vinylic, and alkynyl Grignard reagents using either Fe or Mn catalyst precursors. 49 As Tables 5 and 6 show, this procedure gave excellent results. The most recent contribution to iron-catalyzed cross-coupling, which appeared during the preparation of the ? al draft of this paper, involves application of the old one-pot Barbier procedure in which FeCl3 served as precatalyst and stoichiometric amounts of magnesium turnings and TMEDA additive were used. A mixture of an alkyl and an aryl bromide was added to the mixture of precatalyst, TMEDA, magnesium, and solvent at 0  °C. Good yields of cross-coupled products were obtained. 50 There has been a great deal of activity in the areas of Grignard reagent/o rganic halide cross-coupling and aryl Grignard reagent homocoupling, and the coverage in this essay, whose focus is on the historical aspects, is far from exhaustive. Attention is called to the 2005 review by Frisch and Beller51 and especially (49) Cahiez, G. ; Moyeux, A. ; Buendia, J. ; Duplais, C. J. Am. Chem. Soc. 2007, 129, 13789. (50) Czaplik, W. M. ; Mayer, M. ; von Wangelin, A. J. Angew. Chem. , Int. Ed. 2009, 48, 607. (51) Frisch, A. C. ; Beller, M. Angew. Chem. , Int. Ed. 2005, 44, 674. to the recent Accounts of Chemical Research special issue on cross-coupling. 52 Since ? st reported in 1943, the cross-coupling of Grignard reagents with organic halides, thanks to further development by many later workers, has become a broadly applicable, very useful reaction in organic synthesis. There is much more about Grignard reagents that I have not covered: the various procedures used in their preparation, the mechanism of their formation (which is still controversial), the more complex organomagnesium compounds such as bis(cyclopentadienyl)magnesium, magnesium butadiene, and magnesium anthracene, and the many kinds of reactions that Grignard reage nts have been reported to undergo. But this is only a short essay, and so I have been able to cover only a few selected topics, ones which I hope will be of interest to the reader. More information can be found in the books that I have cited earlier. 16 Acknowledgment. My thanks, as always, to Professor Arnold L. Rheingold for the cover ? gure. OM900088Z (52) Acc. Chem. Res. 2008, 41, No. 11, 1439-1564, special issue. A collection of 11 reviews, many of them relevant to the subject matter of the present essay, with useful, up-to-date references. How to cite Grignard Reagent, Papers