A chiral bicyclic bridgehead phosphoramidite (briphos) prepared from 1-aminoindane is a highly efficient and selective ligand for rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to alpha,beta-unsaturated N,N-dimethyl-sulfamoyl imino esters at ambient temperature. This transformation provides a new class of chiral (Z)-gamma,gamma-diaryl-alpha,beta-dehydroamino esters with excellent yield and enantioselectivity.