A Highly Active Palladium Catalyst for Intermolecular Hydroamination. Factors that Control Reactivity and Additions of Functionalized Anilines to Dienes and Vinylarenes was written by Johns, Adam M.;Utsunomiya, Masaru;Incarvito, Christopher D.;Hartwig, John F.. And the article was included in Journal of the American Chemical Society in 2006.COA of Formula: C14H12N2 This article mentions the following:
We report a catalyst for intermol. hydroamination of vinylarenes that is substantially more active for this process than catalysts published previously. With this more reactive catalyst, we demonstrate that additions of amines to vinylarenes and dienes occur in the presence of potentially reactive functional groups, such as ketones with enolizable hydrogens, free alcs., free carboxylic acids, free amides, nitriles, and esters. The catalyst for these reactions is generated from [Pd(η3-allyl)Cl]2 (with or without added AgOTf) or [Pd(CH3CN)4](BF4)2 and Xantphos (9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene), which generates complexes with large P-Pd-P bite angles. Studies on the rate of the C-N bond-forming step that occurs by attack of amine on an η3-phenethyl and an η3-allyl complex were conducted to determine the effect of the bite angle on the rate of this nucleophilic attack. Studies on model η3-benzyl complexes containing various bisphosphines showed that the nucleophilic attack was faster for complexes containing larger P-Pd-P bite angles. Studies of substituted unsym. and unsubstituted sym. model η3-allyl complexes showed that nucleophilic attack on complexes ligated by Xantphos was faster than on complexes bearing ligands with smaller bite angles and that nucleophilic attack on unsym. allyl complexes with larger bite angle ligands was faster than on unsym. allyl complexes with smaller bite angle ligands. However, monitoring of catalytic reactions of dienes by 31P NMR spectroscopy showed that the concentration of active catalyst was the major factor that controlled rates for reactions of sym. dienes catalyzed by complexes of phosphines with smaller bite angles. The identity of the counterion also affected the rate of attack:reactions of allylpalladium complexes with chloride counterion occurred faster than reactions of allylpalladium complexes with triflate or tetrafluoroborate counterion. As is often observed, the dynamics of the allyl and benzyl complexes also depended on the identity of the counterion. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3COA of Formula: C14H12N2).
4-(Benzylamino)benzonitrile (cas: 10282-32-3) belongs to nitriles. Nitrile compounds can be prepared by the incorporation of a cyanide source through C–C bond formation or by dehydration of primary carboxamides. 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. COA of Formula: C14H12N2
Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts