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使用芳基硼酸酯活化的烷基格氏试剂进行对映选择性铜催化的脱氟烷基化反应

Enantioselective Copper-Catalyzed Defluoroalkylation Using Arylboronate-Activated Alkyl Grignard Reagents.

作者信息

Wang Minyan, Pu Xinghui, Zhao Yunfei, Wang Panpan, Li Zexian, Zhu Chendan, Shi Zhuangzhi

机构信息

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering , Nanjing University , Nanjing 210093 , China.

出版信息

J Am Chem Soc. 2018 Jul 25;140(29):9061-9065. doi: 10.1021/jacs.8b04902. Epub 2018 Jul 10.

DOI:10.1021/jacs.8b04902
PMID:29989802
Abstract

A copper-catalyzed system has been introduced for the enantioselective defluoroalkylation of linear 1-(trifluoromethyl)alkenes through C-F activation to synthesize various gem-difluoroalkenes as carbonyl mimics. For the first time, arylboronate-activated alkyl Grignard reagents were uncovered in this cross-coupling reaction. Mechanistic studies confirmed that the tetraorganoborate complexes generated in situ were the key reactive species for this transformation.

摘要

已经引入了一种铜催化体系,用于通过C-F活化对线性1-(三氟甲基)烯烃进行对映选择性脱氟烷基化反应,以合成各种作为羰基模拟物的偕二氟烯烃。首次在这种交叉偶联反应中发现了芳基硼酸酯活化的烷基格氏试剂。机理研究证实,原位生成的四有机硼酸酯配合物是这种转化的关键反应物种。

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