Generation of unstable carbanions by ligand exchange reaction of sultoxides and application to new synthetic method

研究了利用配体交换反应合成亚砜的新方法，得到了一些有趣的新结果；它们如下。亚砜酰亚氮吡啶与t-BuLi反应生成了收率较高的亚氮吡啶锂。研究了α -二烷基胺衍生物的性质及其在合成中的应用。具有碳离子不稳定基团（烷基）的氧酰锂是由亚酰基氧酰脲的配体交换反应生成的。介绍了含旋光形式环氧化合物和醇类化合物的性质及其在新合成方法中的应用。发现-卤代亚砜与格氏试剂反应生成烷基化镁类碳化合物。该反应为四取代烯烃的合成提供了一种新的方法。实现了一种甲基酯单碳同源化的新方法，并将该方法应用于内酯的单碳扩环和α、β -不饱和醛的同源化。亚砜版的Julia-Lythgou烯烃是通过-甲氧基亚砜的配体交换反应实现的。

Development of new synthetic methods by the ligand exchange reaction of sulfoxides were investigated and several new interesting results were obtained ; those are as follows.1.The reaction of sulfinyl aziridines with t-BuLi resulted in formation of aziridinyllithium in good yields. The property and synthetic application to alpha-dialkylamino acid derivatives were studied.2.Oxiranyllithium having carbanion destabilizing group (alkyl groups) were abled to be generated by the ligand exchange reaction of sulfinyloxirans. Property and applications to new synthetic method of epoxides and alcohols including optically active form were developed.3.alpha-Halovinyl sulfoxides were found to react with Grignard reagents to give magnesium alkylidene carbenoids. A new synthetic method for tetra-substituted olefins was realized by this reaction.4.A new method for one-carbon homologation of methylesters was realized and the method was applied to one-carbon ring expansion of lactones and to a homologation of alpha, beta-unsaturated aldehydes.5.Sulfoxide version of Julia-Lythgou olefination was realized via the ligand exchange reaction of beta-mesyloxy sulfoxides.