A copper-catalyzed asymmetric hydroallylation of readily available vinylsilanes with allylic phosphates in the presence of hydrosilane was developed. These transformations can be performed under mild reaction conditions and provide the useful chiral organosilanes with good to excellent level of enantiocontrol.

Chiral homoallylic boronates are not only deemed to be the precursors of some valuable skeletons that are prevalent in natural products and pharmaceuticals, but also the versatile building blocks by the two versatile boronate and olefin fragment reaction handles. However, the development of a general and economic synthetic approach for their preparation remains an ongoing challenge. Herein, we describe a general copper-catalysed 1,1-difunctionalization of alkynes, consisting of a cascade hydroboration and asymmetric hydroallylation reaction, furnishing a general, economic and concise approach to chiral homoallylic secondary boronates. This catalytic system displays excellent chemo-, regio- and enantioselectivity, and also showcases good functional group tolerance and a broad scope of substrates (> 120 examples). Equally importantly, industrially relevant acetylene and propyne can also be successfully incorporated, laying the foundation for scalable and economic synthetic applications. In addition, the potential of this method is further highlighted through an array of late-stage functionalization of complicated, biologically active molecules and further applications of chiral homoallylic secondary boronates.