Department of Chemistry , The University of Kansas , 2010 Malott Hall, 1251 Wescoe Hall Drive , Lawrence , Kansas 66045 , United States.
Org Lett. 2018 Jul 20;20(14):4191-4194. doi: 10.1021/acs.orglett.8b01566. Epub 2018 Jun 29.
A method where an allyl alcohol is formed from a Tsuji-Trost allylation between a vinyl epoxide and an acyl containing nucleophile is described. Subsequently, a retro-Claisen condensation is utilized as a means of through-space anion relay. The anion relay results in the formation of a reactive carbanion and simultaneously activates an allylic alcohol toward intramolecular Tsuji-Trost cyclopropanation. Hence, in one pot, Tsuji-Trost allylation, retro-Claisen activation, and Tsuji-Trost cyclopropanation are combined to access synthetically useful vinyl cyclopropanes from vinyl epoxides using a mild and operationally simple procedure.
描述了一种通过烯丙醇与酰基亲核试剂之间的 Tsuji-Trost 烯丙基化反应形成烯丙醇的方法。随后，利用逆-Claisen 缩合作为通过空间阴离子接力的手段。阴离子接力导致形成反应性碳负离子，并同时激活烯丙醇进行分子内 Tsuji-Trost 环丙烷化。因此，在一锅反应中，Tsuji-Trost 烯丙基化、逆-Claisen 活化和 Tsuji-Trost 环丙烷化相结合，使用温和且操作简单的方法从乙烯环氧化物中获得具有合成用途的乙烯基环丙烷。
