Cu/chiral phosphoric acid-catalyzed radical-initiated asymmetric aminosilylation of alkene with hydrosilane

The catalytic radical-initiated asymmetric 1,2-aminosilylation of alkene with a hydrosilane under Cu(I)/CPA cooperative catalysis has been developed. This method features the use of hydrosilane as the reductive radical precursor, enabling efficient access to skeletally diverse silicon-containing azaheterocycles including pyrrolidine, indoline and isoindoline bearing an α-tertiary stereocenter with high enantioselectivity. The key to the success includes the use of Cu(I)/CPA cooperative catalyst system and the β-silicon effect of the silyl group to stabilize the in situ generated carbocation intermediate.