4.8 Article

Recyclable Oxofluorovanadate-Catalyzed Formylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes

Journal

CHEMSUSCHEM
Volume 14, Issue 7, Pages 1763-1766

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.202100117

Keywords

amides; carbon dioxide; fluorides; heterogeneous catalysis; silanes

Funding

  1. NSFC [91745104]
  2. NSF of Jiangsu Province [BK20160394]

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An efficient method using oxofluorovanadates as catalysts has been developed for the reductive amination of CO2, resulting in the transformation of various amines into N-formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies indicate a reaction pathway initiated through F-Si interactions, with activated phenylsilane allowing for CO2 insertion and subsequent formation of the target product through amine attack.
An efficient method has been developed for the reductive amination of CO2 by using readily available and recyclable oxofluorovanadates as catalysts. Various amines are transformed into the desired N-formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies based on in situ infrared spectroscopy suggest a reaction pathway initiated through F-Si interactions. The activated phenylsilane allows for CO2 insertion to produce phenylsilyl formate, which undergoes attack by the amine to generate the target product.

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