An Insight into Nitromethane as an Organic Nitrile Alternative Source towards the Synthesis of Aryl Nitriles

Abstract

Directed by an unusual in situ reduction of CuII, our protocol is a simple CuI‐mediated synthesis of aryl nitriles, with inexpensive and readily available nitromethane as the cyanating source, in moderate to good yields. Exhibiting a wide substrate scope, the method involves simple reaction conditions, is additive free with low catalyst loading. The plausible mechanism of cyanation of aryl halides is elucidated by a congregation of three cycles, namely the in situ reduction of CuII species by nitromethane, generation of HCN species from nitromethane and a regular organometallic pathway which releases the nitrile derivative. The detail of the mechanism of generation of CN– from nitromethane is computationally validated. Our protocol holds the distinction of involving a rarely encountered CuI catalytic species as well as facile in situ generation of nucleophilic CN– to yield synthetically useful aromatic nitriles.

Flavin Nitroalkane Oxidase Mimics Compatibility with NOx/TEMPO Catalysis: Aerobic Oxidization of Alcohols, Diols, and Ethers

“…Initially performed by strong acid treatment of the nitronate salt, the oxidative Nef reaction provides an often milder transformation . Nitroalkane reactivity continues to inspire chemists for their versatility in organic synthesis and we took note that nitromethane itself has recently been investigated as a less toxic, more stable, and inexpensive NO x source, as compared to inorganic reagents, for nitrosation, nitration, alkylation, and cyanation. , Here we demonstrate a significant advance in flavin catalysis for synthetically useful oxidative Nef reactions. Furthermore, we report the use of metal-free, flavin-generated NO x for green cooperative catalysis and the compatibility of flavin- and existing NO x /TEMPO-catalytic cycles, to address challenges in fundamental oxidation reactions …”

Synthesis and characterization of a green and recyclable arginine-based palladium/CoFe2O4 nanomagnetic catalyst for efficient cyanation of aryl halides

“…To overcome this problem, several less-toxic metal-free cyanide sources including malononitrile, butyronitrile, acetonitrile, and benzyl cyanide have been reported. 27,28 Aryl halide cyanations have been reported in various publications utilizing various Pd catalysts, including Pd/C, Pd complexes, and Pd(OAc) 2 . [29][30][31][32] However, the main limitations of these catalysts are their recovery and reuse.…”

Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C–CN Bond Cleavage and Cyano Transfer

“…The reported work in this direction includes the oxidative addition of C–CN to stoichiometric metal complexes by Yamamoto’s and Jones’ groups, the intramolecular aryl cyanation by Nakao’s group, as well as the investigation described by a few other research groups. Nonetheless, regio-selectivity or configuration selectivity in most cases still troubled chemists in their synthesis of alkenyl nitriles through hydrocyanation of alkynes (Scheme A).…”