Copper-catalyzed vinylsilane cross-coupling reactions

Silicon-based cross-coupling reactions are extremely powerful tools for the introduction of new C−C bonds in complex organic frameworks. The ready availability, low cost, and high chemical stability of silylated molecules led to a rapid development of several metal-based cross-couplings. Over the past few years, our group has developed an efficient copper-catalyzed method to functionalize vinylsilanes. This cross-coupling reaction leads to the synthesis of stereodefined alkenes that remain a constant challenge in organic chemistry. Using copper(I) salts and tetrabutylammonium polyfluorides as activating agents, various cis, trans, and 1,1’-disubstituted vinylsilanes could be functionalized. Alkenyl-, allyl- and benzyl-halides could be employed to yield their corresponding cross-coupling products. Full retention of stereochemistry was observed in all cases and sensitives groups such as aldehydes were fully tolerated. This very mild method led to the stereoselective synthesis of very sensitive building blocks that are present in natural products, pharmacologically active molecules, agrochemicals, and materials for optics and electronics.