Preparation of Organocupper Species Using Silyl Migration and Their Application to Organic Synthesis

本论文研究了硅基转移法制备有机铜的方法及其在有机合成中的应用。我们发现，含有羟基的乙烯基硅烷通过1，3-和1，4-Brook型重排，在叔丁氧基铜的作用下，很容易得到乙烯基铜物种。结果表明，铜(I)醇盐的使用和烷氧基的分子内配位作用形成了硅酸盐，促进了这些反应的进行。即使在质子源存在的情况下，维铜物种也能与各种有机卤化物反应生成偶联产物。这种硅基重排反应适用于由α-和β-Silyl-α，β-不饱和酮和铜(I)叔丁醇制得的铜(I)烯醇酸盐，生成具有烯醇硅基结构的乙烯基铜物种；通过有机铜物种与有机卤化物的反应，通过立体选择性地形成烯醇硅基醚，形成C-C键。我们还证明了在没有有机卤化物的情况下，β-三苯基硅烯丙基醇的铜(I)烷氧化物通过硅酸盐的彼得森消除得到了烯丙烯。这是第一个以乙烯基位的Peterson消除反应导致联烯形成的例子。即使当β-三苯基硅烯丙基醇被BuLi作为助溶剂处理时，Peterson消除仍在进行。在此基础上，通过α-硫代乙烯基硅烷和羰基化合物的Pereson烯化反应，发展了一种直接的羰基烯丙化方法。

In this research, preparation methods of organocupper species using O^<sp2>-to-O silyl migration and applications of their organocopper species to organic synthesis were studied. We found that vinylcopper species were readily prepared from vinylsilanes having a hydroxyl group via the 1,3-and 1,4-Brook-type rearrangement by treatment with copper(I) t-butoxide. It was suggested that these reactions were promoted by the combination of the use of copper(I) alkoxides and the formation of silicates by the intramolecular coordination of the alkoxide group. The vinycopper species reacted with various organic halides even in the presence of a proton source to give coupling products. The present silyl rearrangement is applicable to copper(I) enolates prepared from either α-and β-silyl-α,β-unsaturated ketones and copper(I) t-butoxide to produce the vinylcopper species having enol silyl moiety ; by the reaction of the organocopper species with organic halide, the C-C bond formation was achieved with stereoselective formation of the enol silyl ether.We also demonstrated that allenes were obtained by the Peterson elimination of copper(I) alkoxides of β-triphenylsilylallylic alcohols through the formation of the silicate in the absence of the organic halides. This is the first example of the Peterson elimination at a vinylic position leading to the formation of allenes. The Peterson elimination proceeded even when the β-triphenylsilylallylic alcohols were treated with BuLi by virtue of DMF as a cosolvent. Based on this result, a straightforward carbonyl allenation method was developed by the Pereson olefination of α-lithiovinylsilanes and carbonyl compounds.