Geometry-Constrained <i>N</i>,<i>N</i>,<i>O</i>-Nickel Catalyzed α-Alkylation of Unactivated Amides via a Borrowing Hydrogen Strategy
Xue Yang, Xiaoyu Tian, Nan Sun, Baoxiang Hu, Zhenlu Shen, Xinquan Hu, Liqun Jin
Abstract
Reported herein is a well-defined geometry-constrained tridentate N,N,O-nickel complex for selective α-alkylation of unactivated amides using readily available alcohols as the alkylating reagents. The newly developed transformation could accommodate a broad substrate scope including various substituted benzylic or aliphatic alcohols and tertiary/secondary acyclic amides or lactams. The tolerance of methanol and ethanol in this protocol provided a novel possibility of carbon chain homologation of amides. Mechanistic studies suggested that the reaction proceeds through a borrowing hydrogen pathway.
Topics & Concepts
ChemistryAlkylationReagentCatalysisMethanolNickelHydrogenHydrogen fluorideSubstrate (aquarium)Combinatorial chemistryEthanolOrganic chemistryMedicinal chemistryGeologyOceanographyAsymmetric Hydrogenation and CatalysisChemical Synthesis and AnalysisCarbon dioxide utilization in catalysis