Cao, Shanshan published the artcileA mechanistic investigation into N-heterocyclic carbene (NHC) catalyzed umpolung of ketones and benzonitriles: is the cyano group better than the classical carbonyl group for the addition of NHC?, Quality Control of 1885-29-6, the main research area is ketone nitrile cyclocondensation reaction mechanism activation free energy.
D. functional theory (DFT) computations have been utilized to investigate the N-heterocyclic carbene (NHC) catalytic reaction mechanism when carbonyl and cyano compounds co-exist. The results suggested that both the carbonyl and cyano compounds can be activated by NHC, while the order of activation by the NHC depends on the substituents of the two compounds In the model reaction of NHC catalyzed cyclocondensation of cyclohexanone with 2-aminobenzonitrile, two key activation modes were explored, the new NHC activation carbon of the cyano-group (Mode II) is found to be perferred over the activation of carbonyl carbon (Mode I); this is remarkably at variance from the previous reports. More importantly, water mols. can improve the catalytic activity of NHC to some extent, especially in the Dimroth rearrangement process. The cooperative participation of the NHC and H2O catalyst is identified. Moreover, the strong quadruple hydrogen bonding interactions between water/NHC and substrates are proposed to be the origin of the high activity of NHC-H2O co-catalyzed Mode II. Addnl., these interactions stabilize the generated neg. charge on carbonyl oxygen and further strengthen the nucleophilicity of the -NH group in the NHC-H2O co-catalyzed key transition state structure, which is further confirmed by AIM and NCI analyses. This novel preferred umpolung of a cyano-group via NHC-H2O catalysis was proposed to be responsible for the exptl. observed high product yield.
Organic Chemistry Frontiers published new progress about Bader electron density. 1885-29-6 belongs to class nitriles-buliding-blocks, name is 2-Aminobenzonitrile(Flakes or Chunks), and the molecular formula is C7H6N2, Quality Control of 1885-29-6.
Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts