Metal-mediated C-CN Bond Activation in Organic Synthesis

Nitriles are ubiquitous versatile building blocks in organic synthesis. Common reactions of nitriles include the transformation of cyano groups into carbonyl and amine moieties. The functionalization of nitriles can also be accomplished at the alpha-position of alkanenitriles and at the ortho-positi...

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Bibliographic Details
Published in:Chemical reviews 2021-01, Vol.121 (1), p.327-344
Main Author: Nakao, Yoshiaki
Format: Article
Language:English
Subjects:
Alkanes
Carbonyl compounds
Carbonyls
Chemical bonds
Chemical reactions
Chemical synthesis
Coordination compounds
Cross coupling
Cyanide
Cyano groups
Metal complexes
Nitriles
Organometallic compounds
Transformations
Transition metal compounds
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Summary:Nitriles are ubiquitous versatile building blocks in organic synthesis. Common reactions of nitriles include the transformation of cyano groups into carbonyl and amine moieties. The functionalization of nitriles can also be accomplished at the alpha-position of alkanenitriles and at the ortho-position of cyanoarenes. On the other hand, the C-CN bond of nitriles has rarely been recognized as a valuable reaction site due to its thermodynamic robustness. Although it has been known for a long time in organometallic chemistry that C-CN bonds can be cleaved by transition-metal complexes, this elemental reaction had not been used in catalytic synthetic transformations of nitriles until two decades ago. This review surveys the progress of metal-catalyzed reactions of nitriles via C-CN bond activation. After introducing several different modes to activate C-CN bonds by various transition metals, catalytic reactions are categorized mainly into two parts: (i) reactions with CN as a leaving group and (ii) reactions with nitriles as a source of CN groups. Cross-coupling-type transformations with a cyano leaving group, cyanation reactions using nitriles as a nontoxic cyano source, and novel synthetic reactions such as carbocyanation are highlighted together with useful demonstrations of their utility in organic synthesis.
ISSN:0009-2665
1520-6890
DOI:10.1021/acs.chemrev.0c00301