Rhodium-Catalyzed Intermolecular trans-Disilylation of Alkynones with Unactivated Disilanes.

Disilylation of alkynes could provide rapid entry to synthetically useful 1,2-bissilyl-alkenes, but is currently limited to activated disilanes reacting in an intramolecular fashion. Reported herein is an efficient rhodium(I)-catalyzed intermolecular disilylation of a wide array of alkynones with unactivated disilanes. Importantly, this reaction produces exclusively trans-disilylation products, selectivity that has been rarely reported. These disilylation products were transformed into interesting pentacyclic vinyl silane ethers, among other additional synthetic manipulations. Mechanistic studies uncovered that the unactivated disilanes underwent facile Si-Si activation and crossover under the reaction conditions.