可控非对映选择性环丙烷化反应。通过手性碲叶立德实现乙烯基环丙烷的对映选择性合成。

Controllable diastereoselective cyclopropanation. Enantioselective synthesis of vinylcyclopropanes via chiral telluronium ylides.

作者信息

Liao Wei-Wei, Li Kai, Tang Yong

机构信息

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China.

出版信息

J Am Chem Soc. 2003 Oct 29;125(43):13030-1. doi: 10.1021/ja036254c.

DOI:10.1021/ja036254c

PMID:14570468

Abstract

Novel chiral telluronium salts 1 are designed for asymmetric synthesis of 1,3-disubstituted 2-vinylcyclopropanes. The allylides, generated in situ from the corresponding telluronium salt in the presence of different base, reacted with alpha,beta-unsaturated esters, ketones, and amides to afford cis-2-silylvinyl-trans-3-substituted or trans-2-silylvinyl-trans-3-substituted cyclopropane derivatives with high diastereoselectivity and excellent enantioselectivity in good to high yields. Thus, either one of the two diastereomers could be enantioselectively synthesized at will just by the choice of LiTMP/HMPA or LDA/LiBr. The first examples of catalytic ylide reaction for enantioselective synthesis of 1,3-disubstituted 2-vinylcyclopropanes with high distereoselectivity is also achieved.

摘要

新型手性碲鎓盐1被设计用于1,3 - 二取代2 - 乙烯基环丙烷的不对称合成。在不同碱存在下，由相应的碲鎓盐原位生成的烯丙基叶立德与α,β - 不饱和酯、酮和酰胺反应，以良好至高产率得到具有高非对映选择性和优异对映选择性的顺式 - 2 - 硅基乙烯基 - 反式 - 3 - 取代或反式 - 2 - 硅基乙烯基 - 反式 - 3 - 取代的环丙烷衍生物。因此，仅通过选择LiTMP/HMPA或LDA/LiBr，就可以随意对映选择性地合成两种非对映异构体中的任何一种。还实现了用于对映选择性合成具有高非对映选择性的1,3 - 二取代2 - 乙烯基环丙烷的催化叶立德反应的首例。