Premium
An Insight into Nitromethane as an Organic Nitrile Alternative Source towards the Synthesis of Aryl Nitriles
Author(s) -
Saikia Rakhee,
Dey Baruah Satyajit,
Deka Ramesh C.,
Thakur Ashim J.,
Bora Utpal
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201900909
Subject(s) - nitromethane , chemistry , nitrile , cyanation , aryl , catalysis , nucleophile , combinatorial chemistry , aryl halide , organic chemistry , yield (engineering) , palladium , alkyl , materials science , metallurgy
Directed by an unusual in situ reduction of Cu II , our protocol is a simple Cu I ‐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 Cu II 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 Cu I catalytic species as well as facile in situ generation of nucleophilic CN – to yield synthetically useful aromatic nitriles.