Highly enantioselective access to chiral chromanes and thiochromanes via Cu-catalyzed hydroamination with anthranils

A Cu(i)/(R,R)-Ph-BPE-catalyzed enantioselective hydroamination of 2H-chromenes and 2H-thiochromenes with anthranils is developed, which enables highly efficient and atom-economical asymmetric access to a series of 4-arylamino chromanes and thiochromanes bearing a benzylic alcohol functionality in high yields (up to 96%) with excellent enantioselectivities (up to 99% ee). These valuable chiral chromane and thiochromane products may act as key intermediates to access nitrogen-, oxygen- and sulfur-containing bioactive compounds with more molecular complexity.