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DOI: 10.1055/a-1499-8943
Cyanide Anions as Nucleophilic Catalysts in Organic Synthesis
Financial support from the Deutsche Forschungsgemeinschaft is gratefully acknowledged.
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Dedicated to Professor Siegfried Blechert on the occasion of his 75th birthday
Abstract
The nucleophilic addition of a cyanide anion to a carbonyl group is the basis for several cyanide-catalyzed organic reactions, which are summarized in this review. Since cyanide is also a good leaving group, it is an excellent catalyst for transacylation reactions. As an electron-withdrawing group, it also stabilizes a negative charge in its α-position, thus allowing the umpolung of aldehydes to formyl anion equivalents. The two leading examples are the benzoin condensation and the Michael–Stetter reaction furnishing α-hydroxy ketones and 1,4-dicarbonyl compounds, which are both catalyzed by cyanides. The review also covers variants like the silyl-benzoin coupling, the aldimine coupling and the imino-Stetter reaction. Moreover, some cyanide-catalyzed heterocyclic syntheses are reviewed.
1 Introduction
2 Nucleophilic Additions
2.1 Cyanohydrin Formation
2.2 Corey–Gilman–Ganem and Related Oxidation Reactions
2.3 Conjugate Addition
2.4 Intramolecular Carbocyanation
3 Transacylation Reactions
3.1 Ester Hydrolysis and Transesterification
3.2 Formation of Amides
3.3 Ketones from Esters
3.4 Esters from Ketones
4 Transformations Involving an Umpolung
4.1 Benzoin Condensation
4.2 Aldimine Coupling
4.3 Michael–Stetter Reaction
4.4 Imino-Stetter Reaction
5 Formation of Heterocycles
5.1 Oxazolines from Isocyanoacetates
5.2 Imidazoles from TosMIC via Oxazolines
5.3 Bargellini Reaction
6 Conclusion
Publication History
Received: 08 April 2021
Accepted after revision: 05 May 2021
Accepted Manuscript online:
05 May 2021
Article published online:
31 May 2021
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