Enantioselective Rhodium-Catalyzed Desymmetric Hydrosilylation of Cyclopropenes

Catalytic hydrosilylation of alkenes ranks as one of the most important academic and industrial synthetic reactions in homogeneous catalysis and organosilicon chemistry. In this work, a highly enantioselective Rh-catalyzed desymmetric hydrosilylation reaction of 1,1-disubstituted cyclopropenes with the promotion of chiral DTBM-SEGPHOS is described. It allows for a straightforward access to potentially valuable chiral organosilicon compounds bearing a carbon quaternary stereocenter in high yields with good diastereo- and enantioselectivities (up to >99:1 d.r. and >99% ee) in a 100% atom-efficient manner from readily available starting cyclopropenes and hydrosilanes.