由L-酒石酸衍生的酮酰胺制备的对映体纯季铵α-三氟甲基-α-烷氧基醛。

Enantiopure quaternary alpha-trifluoromethyl-alpha-alkoxyaldehydes from L-tartaric acid derived ketoamides.

作者信息

Nonnenmacher Jean, Massicot Fabien, Grellepois Fabienne, Portella Charles

机构信息

Université de Reims Champagne-Ardenne, Institut de Chimie Moléculaire de Reims, CNRS UMR 6229, UFR des Sciences Exactes et Naturelles, BP 1039, 51687 Reims Cedex 2, France.

出版信息

J Org Chem. 2008 Oct 17;73(20):7990-5. doi: 10.1021/jo8013403. Epub 2008 Sep 25.

DOI:10.1021/jo8013403

PMID:18816141

Abstract

The diastereoselective nucleophilic trifluoromethylation of a range of ketoamides derived from L-tartaric acid has been studied. TMSCF3 in the presence of a catalytic amount of K2CO3 in DMF has been identified as the conditions leading to the highest diastereoselectivities. A sequential one-pot reaction trifluoromethylation-etherification of the trifluoromethylcarbinol has been developed. Only one further one-pot reaction, ketal hydrolysis-oxidative cleavage, led to the final alpha-trifluoromethylated alpha-alkoxyaldehydes. This procedure was applied to the preparation of a series of enantiopure aryl, heteroaryl, and alkyl alpha-trifluoromethyl-alpha-alkoxyaldehydes.

摘要

对一系列源自L-酒石酸的酮酰胺的非对映选择性亲核三氟甲基化反应进行了研究。已确定在二甲基甲酰胺（DMF）中，在催化量的碳酸钾存在下的三甲基硅基三氟甲烷（TMSCF3）是导致最高非对映选择性的条件。已开发出三氟甲基甲醇的连续一锅法反应三氟甲基化-醚化反应。仅通过一步进一步的一锅法反应，即缩酮水解-氧化裂解，就得到了最终的α-三氟甲基化α-烷氧基醛。该方法被应用于一系列对映体纯的芳基、杂芳基和烷基α-三氟甲基-α-烷氧基醛的制备。