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

本论文主要研究了有机铜物种的制备方法<sp2>及其在有机合成中的应用。我们发现，乙烯基铜物种容易地制备从乙烯基硅烷具有羟基基团通过1，3-和1，4-布鲁克型重排与铜（I）叔丁醇处理。有人建议，这些反应是促进的组合使用的铜（I）的醇盐和形成硅酸盐的分子内协调的醇盐基团。甚至在质子源存在下，乙烯基铜物种与各种有机卤化物反应，得到偶联产物。本发明的甲硅烷基重排适用于由α-和β-甲硅烷基-α，β-不饱和酮和叔丁醇铜（I）制备的烯醇化铜（I），以产生具有烯醇甲硅烷基部分的乙烯基铜物质;通过有机铜物质与有机卤化物的反应，C-C键的形成是通过烯醇硅醚的立体选择性形成来实现的。我们还证明了联烯是通过通过在不存在有机卤化物的情况下形成硅酸盐，制备β-三苯基甲硅烷基烯丙基醇的烷氧基铜（I）。这是第一个例子彼得森消除在乙烯位置导致形成的联烯。当β-三苯基硅基烯丙基醇与BuLi反应时，由于DMF作为助溶剂，Peterson消除反应仍能进行。在此基础上，通过α-锂乙烯基硅烷与羰基化合物的Pereson烯化反应，发展了一种简单的羰基联烯化方法。

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.