4.8 Article

Highly Regio- and Stereoselective Markovnikov Hydrosilylation of Alkynes Catalyzed by High-Nuclearity {Co14} Clusters

Journal

ACS CATALYSIS
Volume 11, Issue 12, Pages 6944-6950

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c01996

Keywords

high-nuclearity clusters; hydrosilylation; regioselectivity; aliphatic alkyne; heterogeneous catalyst

Funding

  1. National Natural Science Foundation of China [21861006, 22061003, 22075056, 21861005]
  2. Guangxi Natural Science Foundation of China [2019GXNSFAA245027]
  3. Guangxi Key RD Program [AB18221005]
  4. BAGUI Scholar Program of Guangxi Province of China [2016A13]
  5. Guangxi science and technology base and special talents [guike AD19110027]
  6. State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources [CMEMR2020-A13]

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This work developed three high nuclearity {Co-14} cluster catalysts, which successfully achieved highly regio- and stereoselective hydrosilylation of alkynes to produce alpha-vinylsilanes. The catalyst exhibited high regioselectivity, especially for electronically unbiased alkyl alkynes, and leaching tests and reusability proved that the reaction is a heterogeneous process.
This work developed three high-nuclearity {Co-14} clusters of C1-C3 with inner [Co-8] backbone fixed by six ambient CoCl2 species. The catalyst C1 exhibited highly regio- and stereoselective hydrosilylation of alkynes with primary and secondary silane to produce alpha-vinylsilanes. More importantly, C1 shows high regioselectivity for electronically unbiased alkyl alkynes, and the alpha-selectivity of some alkyl alkynes has not been achieved in previous reports. Leaching tests and reusability proved that the reaction is a heterogeneous process.

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