Journal of the American Chemical Society · 2014 · 102 citations · 39 references
Natural SciencesChemistryCatalysisComputational ChemistryOrganometallic ChemistryCatalytic MaterialsCatalytic MechanismsMetal Ion CatalysisOrganic SynthesisCatalytic Cycle AnalysisCatalytic Cycle MechanismsCleavageCleavage FormationGrignard Reagent SynthesisImine CatalysisMulti-component ReactionsTransition Metal-catalyzed Synthesis
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.
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