Palladium-Catalyzed Regio- and Stereoselective Hydrosilylation of Electron-Deficient Alkynes

Abstract

Highly regio- and stereoselective hydrosilylation applicable to a broad range of electron-deficient alkynes has been established using palladium catalysis. The synthetic utility of the method has been demonstrated by further transformations of α-silylalkenes, particularly Hiyama coupling and stereoinverting iododesilylation followed by Suzuki-Miyaura coupling, which enables stereodivergent syntheses of α-arylenoates.

Soluble Pt Nanoparticles Stabilized by a Tris‐imidazolium Tetrafluoroborate as Efficient and Recyclable Catalyst for the Stereoselective Hydrosilylation of Alkynes

“…The major product arose from the syn addition that placed the triethylsilyl moiety in gem to the electron‐withdrawing ester group. A similar α‐directing effect of the electron‐withdrawing groups in the addition of silanes to internal triple bonds under platinum, palladium ,. and rhodium .…”

Stereoselective Silylcupration of Conjugated Alkynes in Water at Room Temperature

“…Trost had shown previously that ruthenium catalysts perform hydrosilylations to give Z-b-vinylsilanes. [18] Palladium catalysts were recently found to give highly selective a-silylation of conjugated alkynes, [19] and Ferreira disclosed a method for the regioselective hydrosilylation of internal alkynes using platinum catalysts. [20] Most recently, and most closely analogous to the present work, Molander described a copper-catalyzed introduction of silicon into conjugated alkynes to give E-b-silyl-substituted carbonyl derivatives.…”

A heterogeneous mesoporous silica-supported cyclopentadienyl ruthenium(II) complex catalyst for selective hydrosilylation of 1-hexyne at room temperature

“…Of the available methods for the preparation of organosilicon compounds including vinylsilanes, hydrosilylation of alkynes is the most direct and atom-economical approach [3][4][5][6][7][8][9][10][11][12].…”