4.7 Article

Chromium-catalysed efficient N-formylation of amines with a recyclable polyoxometalate-supported green catalyst

Journal

DALTON TRANSACTIONS
Volume 50, Issue 1, Pages 90-94

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d0dt03300f

Keywords

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Funding

  1. National Natural Science Foundation of China [21871183, 21631007, 21225103]
  2. Doctoral Fund of Ministry of Education of China [20130002110042]
  3. Tsinghua University Initiative Foundation Research Program [20131089204]
  4. State Key Laboratory of Natural and Biomimetic Drugs [K20160202]
  5. Shanghai Institute of Technology

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This research presents a simple and efficient protocol for the formylation of amines using a polyoxometalate-based chromium catalyst, demonstrating excellent activity and chemo-selectivity for primary amines and diamines. The chromium catalyst is potentially non-toxic, environmentally friendly, and safer than commonly used high valence chromium catalysts like CrO3 and K2Cr2O7, with the ability to be recycled multiple times without significant loss of activity. Additionally, a plausible mechanism is proposed based on intermediate observation and control experiments.
A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemo-selectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.

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