Nickel-Catalyzed Cross-Redistribution between Hydrosilanes and Silacyclobutanes

Shaowei Chen; Xiaoqian He; Chenyu Jin; Weilu Zhang; Yuxi Yang; Shanshan Liu; Yu Lan; Kendall N Houk; Xiao Shen

doi:10.1002/anie.202213431

Nickel-Catalyzed Cross-Redistribution between Hydrosilanes and Silacyclobutanes

Angew Chem Int Ed Engl. 2022 Dec 12;61(50):e202213431. doi: 10.1002/anie.202213431. Epub 2022 Nov 10.

Authors

Shaowei Chen¹, Xiaoqian He^{2

3}, Chenyu Jin¹, Weilu Zhang¹, Yuxi Yang¹, Shanshan Liu¹, Yu Lan^{2

3}, Kendall N Houk⁴, Xiao Shen¹

Affiliations

¹ Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Wuhan University, 299 Bayi Road, Wuhan, Hubei, 430072, China.
² School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, 400030, P. R. China.
³ Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, P.R. China.
⁴ Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, USA.

PMID: 36214646
DOI: 10.1002/anie.202213431

Abstract

Silanes are important in chemistry and material science. The self-redistribution of HSiCl₃ is an industrial process to prepare SiH₄ , 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 Ni⁰ -Ni^II -Ni^IV catalytic cycle.

Keywords: Cross-Redistribution; Enthalpy-Driven; Nickel Catalysis; Silacyclobutanes; Silane.

Abstract

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