未活化烯烃与卤代烃的定向铜催化分子间Heck型反应
Directed Copper-Catalyzed Intermolecular Heck-Type Reaction of Unactivated Olefins and Alkyl Halides.
作者信息
Tang Chunlin, Zhang Ran, Zhu Bo, Fu Junkai, Deng Yi, Tian Li, Guan Wei, Bi Xihe
机构信息
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry , Northeast Normal University , Changchun 130024 , China.
Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology , Peking University Shenzhen Graduate School , Shenzhen 518055 , China.
出版信息
J Am Chem Soc. 2018 Dec 12;140(49):16929-16935. doi: 10.1021/jacs.8b10874. Epub 2018 Nov 16.
A new type of intermolecular alkylative olefination of unactivated olefins and alkyl halides has been realized for the first time. This copper-promoted Heck-type reaction employs a directing-group strategy to efficiently produce the coupled alkyl olefin products with excellent regio- and stereoselectivity. A broad substrate scope including 1°, 2°, and 3° alkyl bromides and various nonactivated alkenes could be well tolerated. DFT calculations disclosed a dimethyl sulfoxide assisted concerted H-Br elimination process of a conformationally strained Cu(III) cyclic transition state.
首次实现了一种新型的未活化烯烃与卤代烃之间的分子间烷基化烯烃化反应。这种铜促进的Heck型反应采用导向基团策略，以优异的区域和立体选择性高效地生成偶联的烷基烯烃产物。包括一级、二级和三级烷基溴以及各种未活化烯烃在内的广泛底物范围都能得到良好的耐受。密度泛函理论计算揭示了一种二甲亚砜辅助的构象受限的Cu(III)环状过渡态的协同H-Br消除过程。
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