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(PPh 3 ) 4 ) or Pt 2 (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.