Chiral Carboxylic Acid Enabled Achiral Rhodium(III)-Catalyzed Enantioselective C-H Functionalization
Chiral Carboxylic Acid Enabled Achiral Rhodium(III)-Catalyzed Enantioselective C-H Functionalization
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DOI：
10.1002/anie.201807610
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发表时间：
2018-09-10
影响因子：
16.6
通讯作者：
Matsunaga, Shigeki
中科院分区：
文献类型：
--
作者：
Lin, Luqing;Fukagawa, Seiya;Matsunaga, Shigeki
报道了非手性（CpRhIII）-Rh-x/手性羧酸催化的二芳基甲胺与重氮丙二酸酯的不对称C-H烷基化反应，然后环化和脱羧得到1，4-二氢异喹啉-3（2 H）-酮。仲烷基胺以及未保护的伯烷基胺以高的对映选择性（高达98.5：1.5 e.r.）通过使用新开发的手性羧酸作为手性的唯一来源，通过协调的金属化-去质子化机制实现对映选择性C-H裂解。
Reported is an achiral (CpRhIII)-Rh-x/chiral carboxylic acid catalyzed asymmetric C-H alkylation of diarylmethanamines with a diazomalonate, followed by cyclization and decarboxylation to afford 1,4-dihydroisoquinolin-3(2H)-one. Secondary alkylamines as well as nonprotected primary alkylamines underwent the transformation with high enantioselectivities (up to 98.5:1.5 e.r.) by using a newly developed chiral carboxylic acid as the sole source of chirality to achieve enantioselective C-H cleavage by a concerted metalation-deprotonation mechanism.