SmI2 促进的 Reformatsky 型反应和烷基 1-氯环丙羧酸酯的酰化反应。

SmI2-promoted Reformatsky-type reaction and acylation of alkyl 1-chlorocyclopropanecarboxylates.

机构信息

Department of Chemistry, Faculty of Textile Science and Technology, Shinshu University, Ueda, Nagano 386-8567, Japan.

出版信息

Org Lett. 2008 Dec 4;10(23):5453-6. doi: 10.1021/ol8022038.

DOI:10.1021/ol8022038

Abstract

In the presence of HMPA in THF, highly stereoselective SmI(2)-promoted substitutions of alkyl 1-chlorocyclopropanecarboxylates 1 using various ketones, aldehydes (Reformatsky-type reaction), and acyl chlorides (acylation) proceeded to give trans-adducts (2 or 5) in good to high yield with excellent trans-stereoselectivity (trans-add/cis-add = > 99/1). The Reformatsky-type reaction of 1 with aldehydes and unsymmetrical ketones proceeded with moderate diastereoselectivity (re-face-adduct/si-face-adduct = 60/40-75/25).

摘要

在四氢呋喃中存在 HMPA 的情况下，使用各种酮、醛（Reformatsky 型反应）和酰氯（酰化），高立体选择性地进行 SmI(2)-促进的烷基 1-氯环丙烷羧酸酯 1 的取代反应，以高产率得到反式加成物（2 或 5），具有极好的反式立体选择性（反式加/顺式加>99/1）。1 与醛和不对称酮的 Reformatsky 型反应具有中等的非对映选择性（re-面加合物/si-面加合物=60/40-75/25）。