过氧酯光解脱羧形成手性缩醛和醚过程中的构型保持。

Retention of configuration in photolytic decarboxylation of peresters to form chiral acetals and ethers.

作者信息

Spantulescu M Daniel, Boudreau Marc A, Vederas John C

机构信息

Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2.

出版信息

Org Lett. 2009 Feb 5;11(3):645-8. doi: 10.1021/ol802745n.

DOI:10.1021/ol802745n

PMID:19113895

Abstract

Peresters generate ethers in good yields when photolyzed in the absence of solvent using short wavelength UV light. At -78 degrees C or below, the process proceeds predominantly with retention of configuration at the site adjacent to the carbonyl where the decarboxylation occurs, but increase in temperature results in loss of stereochemical control. Chiral acyclic acetals can be prepared using precursors derived from tartaric or malic acids.

摘要

在无溶剂条件下用短波长紫外光照射时，过氧酸酯能以良好的产率生成醚。在-78℃或更低温度下，该过程主要在羰基邻位发生脱羧反应的位置上以构型保持为主，但温度升高会导致立体化学控制丧失。手性非环状缩醛可使用由酒石酸或苹果酸衍生的前体来制备。