C-CN Bond Cleavage via Oxidative Addition

The ability of low-valent transition metal complexes to activate C-CN bonds via oxidative addition has been known since the 1970s (Eq. (6.15)) [32]. The metalbinding capability of a cyano group, as well as the polarized nature of a C-CN bond, enables this oxidative addition to occur without any assistance from ring strain or a directing group. 

Decarbonylation of acyl cyanides has also been known since Blum reported a rhodium-catalyzed reaction in 1967 (Eq. (6.16)) [35]. Later, this reaction was significantly improved by using a palladium-based catalyst [36]. 

The first such catalytic reaction was reported in 2001 by Miller. Aryl cyanides can be coupled with aryl-, alkyl-, and alkenyl-magnesium halides pretreated with 

Entry Nucleophile Catalyst precur-sor/additive Product References 

Palladium-based catalysts are among the most effective for cross-couplings of aryl halides, but the reactions listed in Table 6.1 can be catalyzed specifically 

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