Lanthanum Ate Amide-Catalyzed Regio- and Stereoselective Hydrosilylation of Internal Alkynes

Silylalkenes are important synthetic intermediates to substituted alkenes and silicon materials and can be directly obtained by the catalytic selective hydrosilylation of alkynes. In this Letter, the catalytic selective α- syn -hydrosilylation of both aryl- and silyl-substituted internal alkynes is described with an ene-diamido rare-earth ate complex as a catalyst. The reaction resulted in the selective formation of trisubstituted silylalkenes, including geminal disilylalkenes. The kinetic study and DFT calculations disclosed crucial roles of ate structure of the lanthanum catalyst for high reactivity.