Carboxamide-Directed Stereospecific Couplings of Chiral Tertiary Alkyl Halides with Terminal Alkynes
Carboxamide-Directed Stereospecific Couplings of Chiral Tertiary Alkyl Halides with Terminal Alkynes
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DOI：
10.1021/acscatal.2c02433
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发表时间：
2022-08
期刊：
影响因子：
12.9
通讯作者：
Hiroki Akagawa;Naoki Tsuchiya;Asuka Morinaga;Y. Katayama;Michinori Sumimoto;T. Nishikata
中科院分区：
文献类型：
--
作者：
Hiroki Akagawa;Naoki Tsuchiya;Asuka Morinaga;Y. Katayama;Michinori Sumimoto;T. Nishikata
本文报道了一种手性α-溴代甲酰胺与炔的Sonogashira立体定向偶联反应，该反应以立体保留的方式生成手性烷基化炔。在该反应中，CuBr/bathophen催化剂体系和羧酰胺导向基团对于实现偶联的高对映体特异性是必不可少的。反应机理研究表明，炔基铜物种是与手性α-溴代甲酰胺的甲酰胺基团配位的关键中间体。
Herein, we report the stereospecific Sonogashira coupling of a chiral α-bromocarboxamide possessing atert-alkyl moiety and an alkyne; this reaction produces a chiraltert-alkylated alkyne in a stereoretentive manner. In this reaction, both the CuBr/bathophen catalyst system and carboxamide directing group are essential for achieving the high enantiospecificities of the couplings. Mechanistic studies of this reaction revealed that the alkynyl copper species is the key intermediate that coordinates to the carboxamide group of chiral α-bromocarboxamide.