镍催化γ,δ-烯基酮亚胺中未活化烯烃的区域和立体选择性烷基芳基化反应
Ni-Catalyzed Regio- and Stereoselective Alkylarylation of Unactivated Alkenes in γ,δ-Alkenylketimines.
作者信息
Aryal Vivek, Chesley Lucas J, Niroula Doleshwar, Sapkota Rishi R, Dhungana Roshan K, Giri Ramesh
机构信息
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802.
出版信息
ACS Catal. 2022 Jun 17;12(12):7262-7268. doi: 10.1021/acscatal.2c01697. Epub 2022 Jun 2.
Abstract
We disclose a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ-alkenylketimines with aryl halides and alkylzinc reagents. The reaction produces γ-C(sp)-branched δ-arylketones with the construction of two new C(sp)-C(sp) and C(sp)-C(sp) bonds. Electron-deficient alkenes play crucial dual roles as ligands to stabilize reaction intermediates and to increase catalytic rates for the formation of C(sp)-C(sp) bonds. This alkene alkylarylation reaction is also effective for secondary alkylzinc reagents and internal alkenes, and proceeds with a complete regio- and stereocontrol, affording products with up to three contiguous all-carbon all- secondary stereocenters.
摘要
我们报道了一种镍催化的γ,δ-烯基酮亚胺中未活化烯烃与芳基卤化物和烷基锌试剂的邻位烷基芳基化反应。该反应通过构建两个新的C(sp³)-C(sp²)和C(sp³)-C(sp³)键生成γ-C(sp³)支链的δ-芳基酮。缺电子烯烃作为配体发挥关键的双重作用，稳定反应中间体并提高形成C(sp³)-C(sp²)键的催化速率。这种烯烃烷基芳基化反应对仲烷基锌试剂和内烯烃也有效，并且具有完全的区域和立体化学控制，可提供含有多达三个连续全碳全仲立体中心的产物。
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