首次从醛以及由烯丙基卤化物和手性硫化物生成的叶立德对乙烯基环氧乙烷进行对映选择性合成。

First enantioselective synthesis of vinyl oxiranes from aldehydes and ylides generated from allyl halides and chiral sulfides.

作者信息

Zanardi Jacques, Lamazure David, Minière Stéphanie, Reboul Vincent, Metzner Patrick

机构信息

Laboratoire de Chimie Moléculaire et Thio-organique (UMR CNRS 6507), ISMRA-Université de Caen, 6 Boulevard du Maréchal Juin, F-14050 Caen, France.

出版信息

J Org Chem. 2002 Dec 13;67(25):9083-6. doi: 10.1021/jo026085z.

DOI:10.1021/jo026085z

PMID:12467434

Abstract

Asymmetric allylidenation of aldehydes with sulfur ylides is possible with proper substitution of the initial sulfide, to avoid the [2,3] sigmatropic rearrangement of the unsaturated ylides. One-pot reaction of (2R,5R)-dimethylthiolane with allyl halides, aldehydes, and sodium hydroxide in tert-butyl alcohol affords vinyl oxiranes in good yields. Enantiomeric excesses up to 90% and trans selectivities have been achieved with methallyl-type halides.

摘要

通过对起始硫化物进行适当取代，醛与硫叶立德的不对称烯丙基化反应是可行的，以避免不饱和叶立德的[2,3] 迁移重排。(2R,5R)-二甲基硫杂环戊烷与烯丙基卤化物、醛和氢氧化钠在叔丁醇中进行一锅反应，可高产率地得到乙烯基环氧乙烷。使用甲基烯丙基型卤化物时，对映体过量可达90% 并具有反式选择性。