Cyanide Anions as Nucleophilic Catalysts in Organic Synthesis

Dedicated to Professor Siegfried Blechert on the occasion of his 75^th 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

Key words

catalysis - cyanide - umpolung - benzoin condensation - Stetter reaction - heterocycles

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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