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.
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Since C(sp)-O bonds are a ubiquitous chemical motif in both natural and artificial organic molecules, the universal transformation of C(sp)-O bonds will be a key technology for achieving carbon neutrality. We report herein that gold nanoparticles supported on amphoteric metal oxides, namely, ZrO, efficiently generated alkyl radicals via homolysis of unactivated C(sp)-O bonds, which consequently promoted C(sp)-Si bond formation to give diverse organosilicon compounds. A wide array of esters and ethers, which are either commercially available or easily synthesized from alcohols participated in the heterogeneous gold-catalyzed silylation by disilanes to give diverse alkyl-, allyl-, benzyl-, and allenyl silanes in high yields.
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CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
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Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623, Berlin, Germany.
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School of Pharmaceutical Sciences and MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Tsinghua University, Beijing, 100084, P. R. China.
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.
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