Cu-catalyzed regiodivergent and stereoselective silylation of 2,3-disubstituted 1,3-dienes

Abstract

Regiodivergent silylation of conjugated dienes represents an elegant and straightforward approach to accessing diverse organosilicon compounds. While the silylation of 1- or 2- substituted conjugated dienes has been well developed, the silylation of sterically more demanding 2,3-disubstituted dienes has not been reported. Here, we developed a Cu-catalyzed regiodivergent protosilylation of 2,3-disubstituted dienes, delivering 2,1- and 4,1-protosilylation products regioselectively and stereoselectively. Moreover, 4,1-borosilylation with excellent regio- and stereoselectivity levels was also achieved in the absence of electrophile under conditions similar to those used for 2,1-protosilylation. Our method can be used to efficiently synthesize structurally diverse organosilicon compounds, and hence help fill in the map of silylated conjugated dienes.