Ring Expansion toward Disila‐carbocycles via Highly Selective C−Si/C−Si Bond Cross‐Exchange
Min Liu, Nuo Yan, Haowen Tian, Bo Li, Dongbing Zhao
Abstract
Herein, we successfully inhibited the preferential homodimerization and C-Si/Si-H bond cross-exchange of benzosilacyclobutenes and monohydro-silacyclobutanes and achieved the first highly selective C-Si/C-Si bond cross-exchange reaction by deliberately tuning the Ni-catalytic system, which constitutes a powerful and atom-economical ring expansion method for preparing medium-sized cyclic compounds bearing two silicon atoms at the ring junction, which are otherwise inaccessible. The DFT calculation explicitly elucidated the pivotal role of Si-H bond at silacyclobutanes and the high ring strain of two substrates in realizing the two C-Si bonds cleavage and reformation in the catalytic cycle.
Topics & Concepts
Ring (chemistry)Ring strainCatalysisChemistryCatalytic cycleBond cleavageSiliconAtom (system on chip)Cleavage (geology)CrystallographyStereochemistryMaterials scienceOrganic chemistryComposite materialFracture (geology)Embedded systemComputer scienceOrganoboron and organosilicon chemistrySynthetic Organic Chemistry MethodsCatalytic Cross-Coupling Reactions