A. Organolithium Reagents(答Organolithium试剂).pdf

A. Organolithium Reagents(答Organolithium试剂).pdf

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A. Organolithium Reagents(答Organolithium试剂)

A. Organolithium Reagents Copyright H. J. Reich 2002 Simple organolithium reagents (MeLi, PhLi, n-BuLi, sec-BuLi, t-BuLi and a few others) are usually made by the reduction of halides, normally chlorides, with lithium. The direct reaction of lithium metal with more complex substrates is difficult. However, several very effective lithium-arene reagents or catalysts (such as 4,4-di-t- butylbiphenyl) have allowed a much wider range of lithium reagents to be prepared by reduction not only of halides, but also of sulfides, epoxides, oxetanes, and other ethers.[17] The principal enabling force in the development of organolithium chemistry is the commercial availability of inexpensive stable solutions of n-butyllithium. Many hundreds of functionalized organolithium reagents have become available by the metalation (Li/H exchange) reaction using n-butyllithium, or the more potent and selective (but also more expensive and difficult to handle) t-butyllithium and sec-butyllithium.[1, 2] R-H + n-BuLi 6 R-Li + n-BuH The scope of the metalation reaction has been expanded by the use of complexing and chelating reagents such as hexamethylphosphoric triamide (HMPA), N ,N ’-dimethylpropyleneurea (DMPU) and tetramethylethylenediamine (TMEDA)[2g] which increase the rate of metalation and thus extend the range of compounds which can be deprotonated. The polar cosolvents can also have substantial effects on the subsequent reactions of the organolithium reagents, e.g., increasing rates of SN2 reactions, and changing ratios of 1,2- to 1,4-addition. However, side reactions such as proton transfers can also be favored by these cosolvents. A variety of potassium reagents can be prepared either by use of potassium hydride[6] or the combination of butyllithium and potassium t-butoxide.[11] Many -heteroatom substituted organolithium reagents have been used

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