A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines
Georgia R. Harris, Aaron Trowbridge, Matthew J. Gaunt
Abstract
A long-standing challenge within radical chemistry is that of controlling the absolute stereochemistry of the products. Here, we report the stereocontrolled addition of α-amino radicals reductively generated from imines via visible-light-mediated photoredox-catalysis to alkenes, giving rise to enantioenriched α-trialkyl-α-tertiary amines. This process exploits a commercially available phenylglycinol derivative as a source of both nitrogen and chiral information. DFT studies support a stereochemical model whereby an intramolecular H-bond rigidifies the transition state of the enantiodetermining step.
Topics & Concepts
ChemistryIntramolecular forcePhotocatalysisPhotoredox catalysisRadicalCatalysisAmine gas treatingDerivative (finance)Combinatorial chemistryPhotochemistryTertiary amineOrganic chemistryEconomicsFinancial economicsRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques