Nickel-catalyzed decyanation of inert carbon–cyano bonds

Abstract

Nickel catalyzed decyanation of aryl and aliphatic cyanides with hydrosilane as the hydride source has been developed. This method is easy to handle, scalable and can be carried out without a glove box. The method has been applied in the cyanide directed functionalization reaction and α-substitution of benzyl cyanide.

The reductive decyanation reaction: an overview and recent developments

“…Maiti et al established that the Ni(acac) 2 complex (acac = acetylacetonate) of PCy 3 (Cy, cyclohexyl) in combination with TMDS (tetramethyldisiloxane) as hydride source can catalyze the reductive decyanation efficiently (method A, Scheme 19 ) [ 104 ]. The use of AlMe 3 appeared beneficial by facilitating the oxidative addition of the C–CN bond to Ni.…”

“… Ni-catalyzed reductive decyanation (method A: 28 examples and 2 synthetic applications; method B: 31 examples and 5 synthetic applications) [ 104 – 105 ]. …”

Transition Metals Catalyzed Element-Cyano Bonds Activations

“…Recently, Maiti disclosed a similar strategy, wherein the hydride source was replaced with TMDSO and metal was changed to Ni(0) (21). And most recently (22), the hydride source was replaced by hydrogen gas (Scheme 16), which made it more valuable for the cleavage of cyano group.…”

Palladium Supported on Nanodiamonds as an Efficient Catalyst for the Hydrogenating Deamination of Benzonitrile and Related Compounds

“…Decyanation processes generally involvet he loss of ac yanide group, [1] resulting in carbon loss. Chemical processes involving the conversion of cyanides to alkanes with the retention of the carbon atom are rarely reported in literature, butd eveloping such am ethod could provide the dual benefito fd ecyanation and alkylation.…”