Efficient and Clean Nickel Catalyzed α‐Allylation Reaction of Nitriles

Abstract

A clean method has been developed for the α‐allylation of phenyl and alpha alkyl phenyl acetonitrile with allylic alcohols. The reaction is catalyzed by nickel complexes in situ generated from a combination of Ni(cod)2 and the dppf ligand and performed at 80 °C in methanol as reaction solvent. Accordingly to this simple and base‐free protocol that only yields water as a side‐product, many allylic nitriles were synthetized with good yields.

Sustainable and selective Ni-catalyzed allylation of 2-oxindoles and 2-coumaranones in batch and flow chemistry

“…In order to prevent waste, allyl alcohol is used as an allylation reagent leading to water as the sole reaction by-product. [35][36][37][38][39] It is also noteworthy that allyl alcohol is industrially produced 40 and is also accessible from vegetal feedstock as glycerol. [41][42][43][44] Depending on the sites that are allylated and the substitution degree, several products are accessible.…”

“…In order to prevent waste, allyl alcohol is used as an allylation reagent leading to water as the sole reaction by-product. 35–39 It is also noteworthy that allyl alcohol is industrially produced 40 and is also accessible from vegetal feedstock as glycerol. 41–44…”

The Selective Nickel‐Catalyzed N‐Allylation of C3‐Unprotected Indoles under Mild and Clean Conditions

“…Nickel appears to be the most promising metal for the replacement of palladium. In that optic, we recently described the clean nickel catalyzed N ‐allylation of amides [11] and C ‐allylation of activated nucleophiles (diketones, ketoesters), [12] malonates, [13] aldehydes, [14] ketones [15] and nitriles [16] . We now wish to describe the clean and highly selective nickel catalyzed N ‐allylation of indoles with allylic alcohols without addition of any additive (Scheme 1).…”

Nickel-Catalyzed Direct Substitution of Allylic Alcohols with Nitriles: A General Tool for the Construction of Acyclic C2-Tertiary or Quaternary Benzyl Nitriles

“…In all cases ( 3l – 3p ), monoallylated products were formed predominantly regardless of the nature of the substituent (aryl or alkyl) at the allyl terminus, which could be easily separated with bis-allylated products through column chromatography. It was noted that the use of 2-fluorobenzonitrile or 2-(naphthalen-2-yl)­acetonitrile provided only bis-allylated products when reacting with prop-2-en-1-ol reported in the literature …”

“…Despite the advances, these reactions have some drawbacks such as the requirement of the CO 2 gas, prelocation of the acetyl or ester group on nitriles, high cost of the catalysts, etc. Very recently, a nickel catalyzed α-allylation of benzyl nitriles has been studied using Ni­(cod) 2 /dppf/MeOH as the catalytic system in the presence of excess amounts of allyl alcohols (3 equiv) . However, the reaction scope is limited since only prop-2-en-1-ol and diphenylacetonitrile were used as the reaction partners when studying the scope of nitriles and allylic alcohols, respectively.…”