钴催化（杂）芳烃与苯乙烯的不对称烷基化反应
Cobalt-Catalyzed Asymmetric Alkylation of (Hetero)Arenes with Styrenes.
作者信息
Qin Tao, Lv Guowei, Miao Huanran, Guan Meihui, Xu Chunlu, Zhang Ge, Xiong Tao, Zhang Qian
机构信息
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
出版信息
Angew Chem Int Ed Engl. 2022 Jun 27;61(26):e202201967. doi: 10.1002/anie.202201967. Epub 2022 May 5.
An efficient and general intermolecular Cobalt(II)-catalyzed asymmetric alkylation of styrenes with (hetero)arenes including indoles, thiophene and electron rich arenes has been developed, providing straightforward access to enantioenriched alkyl(hetero)arenes with high enantioselectivity. Mechanistic studies suggest that the reaction underwent a CoH-mediated hydrogen atom transfer (HAT) with alkenes, followed by a pivotal catalyst-controlled S 2-like pathway between in situ generated organocobalt(IV) species and aromatic nucleophiles. This is the first CoH-catalyzed asymmetric hydrofunctionalization using carbon nucleophiles, providing a new strategy for asymmetric Friedel-Crafts type alkylation.
已开发出一种高效通用的分子间钴（II）催化的苯乙烯与（杂）芳烃（包括吲哚、噻吩和富电子芳烃）的不对称烷基化反应，可直接获得对映体富集的烷基（杂）芳烃，且对映选择性高。机理研究表明，该反应通过钴氢介导的与烯烃的氢原子转移（HAT），随后是原位生成的有机钴（IV）物种与芳族亲核试剂之间关键的催化剂控制的类似S2的途径。这是首次使用碳亲核试剂进行的钴氢催化不对称氢官能化反应，为不对称傅克型烷基化提供了一种新策略。
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