Ligand Relay Catalysis Enables Asymmetric Migratory Reductive Acylation of Olefins or Alkyl Halides

• DOI: 10.1021/jacs.2c10785
• Publication Date: 2022-11-17T18:52:22Z
• Authors: Xiaoli Jiang; Feng-Tao Sheng; Yao Zhang; Gao Deng; Shaolin Zhu
• Keywords: Inorganic Chemicals; Acylation; Alkenes; Ligands; 01 natural sciences; Catalysis; 0104 chemical sciences

Design of ligands in transition-metal catalyzed reactions is challenging, especially in asymmetric transformations. With each step in the catalytic cycle promoted by its privileged ligand and different steps well-connected by dynamic ligand exchange, synergistic combination of multiple ligands could potentially enhance the catalytic efficiency and selectivity. Now, this concept has been applied to the NiH-catalyzed asymmetric remote hydroacylation of olefins and migratory acylation of alkyl halides with excellent regio- and enantioselectivity, utilizing two simple ligands, one for chain-walking and the other for asymmetric acylation. Starting from abundant alkenes/alkyl halides and carboxylic acids, a wide range of enantioenriched chiral α-aryl ketones can be efficiently accessed under mild conditions.