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DOI: 10.1055/s-0033-1338596
The Nef Reaction of Isocyanides
Publication History
Received: 15 October 2013
Accepted after revision: 11 November 2013
Publication Date:
05 March 2014 (online)
Abstract
The interaction of isocyanides with acyl chlorides was first reported by Nef in 1892. The resulting α-keto imidoyl chlorides may be hydrolyzed to form α-keto amides. Relatively few data are available on this reaction and the chemistry of α-keto imidoyl chlorides has been largely underestimated until some recent uses in intra- and intermolecular couplings with a variety of nucleophiles. The present review brings a comprehensive presentation of the Nef reaction of isocyanides focusing on mechanism and regioselectivity issues.
1 Isocyanide Chemistry
2 Isocyanide Interaction with Acyl Chlorides and Analogues
2.1 General Considerations
2.2 Methods of Preparation of α-Keto Imidoyl Chlorides
2.3 Nef Reaction Mechanism
3 Reactivity of α-Keto Imidoyl Chlorides
3.1 General Behavior of α-Keto Imidoyl Chlorides
3.2 Intramolecular Trappings
3.3 Intermolecular Trappings and Three-Component Reactions
4 Extensions of the Nef Reaction
5 Conclusion
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For reviews concerning Ugi couplings, see: