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Nickel‐Catalyzed Cross‐Redistribution between Hydrosilanes and Silacyclobutanes

Shaowei Chen, Xiaoqian He, Chenyu Jin, Weilu Zhang, Yuxi Yang, Shanshan Liu, Yu Lan, K. N. Houk, Xiao Shen

2022Angewandte Chemie International Edition31 citationsDOI

Abstract

Abstract Silanes are important in chemistry and material science. The self‐redistribution of HSiCl 3 is an industrial process to prepare SiH 4 , which is widely used in electronics and automobile industries. However, selective silane cross‐redistribution to prepare advanced silanes is challenging. We now report an enthalpy‐driven silane cross‐redistribution to access bis‐silanes that contain two different types of Si−H bonds in the same molecule. Compared with entropy‐driven reactions, the enthalpy‐driven reaction shows high regioselectivity, broad substrate scope (62 examples) and high atom economy. Our combined experimental and computational study indicates that the reaction proceeds through a Ni 0 ‐Ni II ‐Ni IV catalytic cycle.

Topics & Concepts

Redistribution (election)SilanesSilaneCatalysisNickelRegioselectivityEnthalpyChemistryMoleculeComputational chemistryMaterials scienceChemical engineeringOrganic chemistryThermodynamicsPolitical scienceEngineeringPhysicsPoliticsLawOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods
Nickel‐Catalyzed Cross‐Redistribution between Hydrosilanes and Silacyclobutanes | Litcius