Three-Component Asymmetric Ni-Catalyzed 1,2-Dicarbofunctionalization of Unactivated Alkenes via Stereoselective Migratory Insertion
Three-Component Asymmetric Ni-Catalyzed 1,2-Dicarbofunctionalization of Unactivated Alkenes via Stereoselective Migratory Insertion
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DOI：
10.1021/jacs.2c06636
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发表时间：
2022-10-12
影响因子：
15
通讯作者：
Engle, Keary M.
中科院分区：
文献类型：
--
作者：
Apolinar, Omar;Kang, Taeho;Engle, Keary M.
公开了在镍/双恶唑啉催化下用芳基碘和芳基/链烯基硼酸酯对未活化烯烃的不对称1，2-二碳官能化。广泛的芳基和烯基亲核试剂是容许的，提供良好的产率和高的对映体选择性的产品。除了末端烯烃，1，2-二取代的内烯烃参与反应，建立两个连续的立体中心，具有高的非对映选择性和中等的对映选择性。实验和计算技术的结合揭示了催化转化的机制，指向一个封闭的壳层途径与antirodetermining迁移插入步骤，立体诱导产生的空间体积庞大的非手性磺酰胺导向基团和半不稳定的双齿配体之间的协同作用。
An asymmetric 1,2-dicarbofunctionalization of unactivated alkenes with aryl iodides and aryl/alkenylboronic esters under nickel/bioxazoline catalysis is disclosed. A wide array of aryl and alkenyl nucleophiles are tolerated, furnishing the products in good yield and with high enantioselectivity. In addition to terminal alkenes, 1,2-disubstituted internal alkenes participate in the reaction, establishing two contiguous stereocenters with high diastereoselectivity and moderate enantioselectivity. A combination of experimental and computational techniques shed light on the mechanism of the catalytic transformation, pointing to a closed-shell pathway with an enantiodetermining migratory insertion step, where stereoinduction arises from synergistic interactions between the sterically bulky achiral sulfonamide directing group and the hemilabile bidentate ligand.