Bioinspired Iron-Catalyzed Dehydration of Aldoximes to Nitriles: A General N-O Redox-Cleavage Method.

Abstract

Inspired by OxdA that operates biocatalytic aldoxime dehydration, we have developed an efficient iron catalyst, Cp*Fe(1,2-Cy2PC6H4O) (1), which rapidly converts various aliphatic and aromatic aldoximes to nitriles with release of H2O at room temperature. The catalysis involves redox activation of the N-O bond by a 1e- transfer from the iron catalyst to the oxime. Such redox-mediated N-O cleavage was demonstrated by the isolation of a ferrous iminato intermediate from the reaction of the ketoxime substrate. This iron-catalyzed acceptorless dehydration approach represents a general method for the preparation of nitriles, and it also delivers salicylonitriles by catalyzing the Kemp elimination reaction.

• Authors: Hongjie Gao, Jia-Yi Chen, Zhiqiang Peng, Lei Feng, Chen-Ho Tung, Wenguang Wang
• Journal: The Journal of organic chemistry (J Org Chem) Vol. 87 Issue 16 Pg. 10848-10857 (08 19 2022) ISSN: 1520-6904 [Electronic] United States
• PMID: 35914249 (Publication Type: Journal Article, Research Support, Non-U.S. Gov't)

Chemical References

• Nitriles
• Oximes
• Iron
• Hydro-Lyases

Topics

• Catalysis
• Dehydration
• Humans
• Hydro-Lyases (chemistry)
• Iron (chemistry)
• Nitriles (chemistry)
• Oxidation-Reduction
• Oximes (chemistry)