Mn-Catalyzed Three-Component Reactions of Imines/Nitriles, Grignard Reagents, and Tetrahydrofuran: An Expedient Access to 1,5-Amino/Keto Alcohols

Abstract

An expedient Mn-catalyzed three-component synthesis of 1,5-amino/keto alcohols from Grignard reagents, imines/nitriles, and tetrahydrofuran (THF) is described, which deviates from the classic Grignard addition to imines/nitriles in THF solvent. THF is split and "sewn" in an unprecedented manner in the reaction, leading to the formation of two geminal C-C bonds via C-H and C-O cleavage. Mechanistic experiments and DFT calculations reveal radical and organo-Mn intermediates in the catalytic cycle and the α-arylative ring-opening of THF as the key reaction step.