Amination with Pd-NHC Complexes: Rate and Computational Studies Involving Substituted Aniline Substrates was written by Hoi, Ka Hou;Calimsiz, Selcuk;Froese, Robert D. J.;Hopkinson, Alan C.;Organ, Michael G.. And the article was included in Chemistry – A European Journal in 2012.Application of 319016-04-1 The following contents are mentioned in the article:
The amination of aryl chlorides with various aniline derivatives using the N-heterocyclic carbene-based Pd complexes Pd-PEPPSI-IPr and Pd-PEPPSI-IPent (PEPPSI=pyridine, enhanced precatalyst, preparation, stabilization, and initiation; IPr=diisopropylphenylimidazolium derivative; IPent= diisopentylphenylimidazolium derivative) has been studied. Rate studies have shown a reliance on the aryl chloride to be electron poor, although oxidative addition is not rate limiting. Anilines couple best when they are electron rich, which would seem to discount deprotonation of the intermediate metal ammonium complex as being rate limiting in favor of reductive elimination. In previous studies with secondary amines using PEPPSI complexes, deprotonation was proposed to be the slow step in the cycle. These exptl. findings relating to mechanism were corroborated by computation. Pd-PEPPSI-IPr and the more hindered Pd-PEPPSI-IPent catalysts were used to couple deactivated aryl chlorides with electron poor anilines; while the IPr catalysis was sluggish, the IPent catalyst performed extremely well, again showing the high reactivity of this broadly useful catalyst. This study involved multiple reactions and reactants, such as 4-((4-Methoxyphenyl)amino)benzonitrile (cas: 319016-04-1Application of 319016-04-1).
4-((4-Methoxyphenyl)amino)benzonitrile (cas: 319016-04-1) belongs to nitriles. There has been no report on the microbial biosynthesis of nitriles and the physiological function of such enzymes, nor was it not even known whether aliphatic and aromatic nitriles are biological compounds or just petrochemicals. Alkyl nitriles are sufficiently acidic to undergo deprotonation of the C-H bond adjacent to the CN group.Strong bases are required, such as lithium diisopropylamide and butyl lithium. The product is referred to as a nitrile anion. Application of 319016-04-1
Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts