金鸡纳生物碱催化炔基酮与三甲基硅基三氟甲烷的不对称三氟甲基化反应。

Cinchona alkaloid-catalyzed asymmetric trifluoromethylation of alkynyl ketones with trimethylsilyl trifluoromethane.

机构信息

Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.

出版信息

Org Lett. 2010 Nov 19;12(22):5104-7. doi: 10.1021/ol102189c. Epub 2010 Oct 18.

DOI:10.1021/ol102189c

PMID:20954725

Abstract

The first catalytic enantioselective trifluoromethylation of alkynyl ketones 1 with (trifluoromethyl)trimethylsilane is disclosed by an operationally simple procedure, based on the combination of ammonium bromide of bis-cinchona alkaloids with Me(4)NF to afford trifluoromethyl-substituted tertiary propargyl alcohols (up to 96% ee), which are the important chiral building blocks for pharmaceuticals. Biologically attractive aryl heteroaryl trifluoromethyl carbinols were also synthesized.

摘要

首次报道了通过操作简单的方法，基于双金鸡纳碱的溴化铵与 Me(4)NF 的组合，实现了炔基酮 1 与 (三氟甲基)三甲基硅烷的首次催化对映选择性三氟甲基化，得到了三氟甲基取代的叔炔丙醇（高达 96%ee），这是药物合成中的重要手性砌块。还合成了具有生物吸引力的芳基杂芳基三氟甲基碳醇。