Novel Carbon-Carbon Bond Formation Utilizing Selective C-H Bond Insertion by Carbenes.

1988:(1)研究了多种碳烯在区域选择性碳氢插入或烷氧化合物中的最佳反应条件。(2)除烷氧化合物外，还研究了其他被碳烯选择性插入的底物。烯醇酸阴离子、腈碳离子和烷基锂离子可选择性插入-碳氢键。1989:(3)发现了t-BuOK在低温下对溴代烷类化合物反应的促进作用，并对其作为碳源的反应性进行了研究。(4)环丙醇衍生物如环丙酮半缩醛和氰醇与无负载羰基反应，得到新型开环丙酸环加合物，收率高。(5)研究了一种新型的环乙基碳烯-亲核试剂的三组分联合反应，发现氧鎓化物中间体的生成是该反应的关键步骤。

1988: (1) Optimized reaction conditions for regioselective C-H insertion or alkoxides by a variety of carbenes were examined. (2) In addition to alkoxides, other substrates which undergo selective insertion by carbenes were investigated. Enolate anion, nitrile carbanion, and alkyllithium were found to undergo selective - C-H insertion.1989: (3) Promotion effect of t-BuOK on the reaction of bromolithiocarbenoids at low temperatures was found and their reactivity as carbene sources was investigated. (4) Reaction of cyclopropanol derivatives such as cyclopropanone hemiacetals and cyanohydrins with unencumbered carbenes yielded novel ring-opened cycloadduct propionates in high yields. (5) A novel-type of three-component joint reactions between cyclic etliercarbene - nucleophile was investigated to find that the formation of oxonium ylide intermediate is the key step of this reaction.