RTAD与烯烃的烯反应中溶剂依赖性变化：作为机理探针的环丙基

Solvent-dependent changes in the ene reaction of RTAD with alkenes: the cyclopropyl group as a mechanistic probe.

作者信息

Roubelakis Manolis M, Vougioukalakis Georgios C, Angelis Yiannis S, Orfanopoulos Michael

机构信息

Department of Chemistry, University of Crete, Greece.

出版信息

Org Lett. 2006 Jan 5;8(1):39-42. doi: 10.1021/ol052342l.

DOI:10.1021/ol052342l

PMID:16381562

Abstract

[reaction: see text] The vinylcyclopropyl moiety was used as an efficient probe to test mechanistic possibilities of the triazolinedione-alkene ene reaction. In non-hydroxylic solvents, this reaction afforded only the ene adducts via a closed three-membered aziridinium imide (AI) intermediate, whereas in hydroxylic solvents a dipolar intermediate is favored and trapped by the cyclopropyl moiety to form the corresponding cyclopropyl-rearranged solvent-trapped adducts.

摘要

[反应：见正文] 乙烯基环丙基部分被用作一种有效的探针，以测试三唑啉二酮 - 烯烃烯反应的机理可能性。在非羟基溶剂中，该反应仅通过封闭的三元氮杂环丙烷酰亚胺（AI）中间体生成烯加成物，而在羟基溶剂中，偶极中间体更受青睐，并被环丙基部分捕获，形成相应的环丙基重排溶剂捕获加成物。