Copper-catalyzed anti-stereoselective 1,2-silylamination of alkynes†

Abstract

Highly substituted alkenes are important synthetic intermediates in pharmaceuticals, and the development of such compounds provides a variety of potential alkene monomers for functional polyolefin molecules. At present, a series of syn addition multi-substituted alkenes have been prepared through classical polar addition reactions between alkynes and silylmetal species. However, there is no effective pathway for the anti-selective difunctionalization of alkynes. To the best of our knowledge, there are no reports on the introduction of anti C–Si/C–Het bonds in one step to construct the corresponding difunctional alkenes. Herein, we explore the anti-selective 1,2-silylamination of alkynes by combining the addition of silyl radicals to unsaturated C–C triple bonds with copper chelate-assisted functionalization of vinyl radicals. The successful preparation of a wide array of anti-silylaminated alkene derivatives, including those involving biologically active patterns, fully validates the generality and universality of this protocol. In addition, multi-dimensional mechanism research experiments and derivatization reactions have fully explored the details and application prospects of this transformation.