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

• DOI: 10.1021/ja503520t
• Publication Date: 2014-04-22T16:03:42Z
• Authors: Ruoyu He; Xiqing Jin; Hui Chen; Zhi-Tang Huang; Qi-Yu Zheng; Congyang Wang
• Keywords: Tetrahydrofuran; Geminal; Catalytic cycle; Grignard reaction

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 the classic addition to imines/nitriles in THF solvent. split "sewn" an unprecedented manner reaction, leading formation two geminal C-C bonds via C-H C-O cleavage. Mechanistic experiments DFT calculations reveal radical organo-Mn intermediates catalytic cycle α-arylative ring-opening as key reaction step.