Synthesis of silylbut-1-en-3-ynes and buta-1,3-dienes as building blocks via hydrosilylation of 1,4-bis(trimethylsilyl)buta-1,3-diyne

Abstract

The selective and efficient synthesis of (E)-1,2,4-trisilylbut-1-en-3-ynes obtained via Pt-catalyzed hydrosilylation of 1,4-bis(trimethylsilyl)buta-1,3-diyne is described. Optimized reaction conditions (Pt(PPh3)4) or Pt2(dvs)3, 100 °C, toluene, 18 h) yielded compounds with high isolation yields (76–95%). The modification of (E)-1,2,4-trisilylbut-1-en-3-ynes was further tested in protodesilylation, halodesilylation, hydrosilylation, and Pd-based cross-coupling reactions, resulting in a broad spectrum of new products. These compounds represent new families of buta-1,3-dienes, (E,E)-2,3-bissilylbuta-1,3-dienes, (E,E)-1,2,3-trisilylbuta-1,3-dienes, and (E,E)-1,2,3-trisilylbuta-1,3-dienes, which are ideally suited to silicon-based transformations and are perfect models for the investigation of the reactivity of one silyl group in the presence of another.