36809-32-2Relevant articles and documents
Synthesis, Structure, and Reactivity of Palladium Proazaphosphatrane Complexes Invoked in C-N Cross-Coupling
Matthews, Adrian D.,Gravalis, Gregory M.,Schley, Nathan D.,Johnson, Miles W.
, p. 3073 - 3078 (2018)
The preparation and reactivity of elusive palladium proazaphosphatrane complexes that represent putative intermediates in C-N cross-coupling reactions are described. Variable transannulation in these compounds, as determined by X-ray crystallography, vali
Transition-Metal-Free Diarylation of Isocyanates with Arynes
Jang, Woo Cheol,Hwang, Dong Wook,Seo, Jeong Hoon,Ko, Haye Min
supporting information, (2019/08/30)
A facile method for the transition-metal-free diarylation of isocyanates with arynes in the presence of cesium fluoride has been developed, which affords functionalized diaryl amines in moderate to excellent yields. This reaction has good functional group tolerance and provides excellent regioselectivity by utilizing a methoxy-substituted aryne precursor.
Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination
Arrechea, Pedro Luis,Buchwald, Stephen L.
supporting information, p. 12486 - 12493 (2016/10/07)
Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross-coupling reactions for a range of aryl halides and diarylamines. Hammett plots demonstrated that Pd(II) amido complexes derived from electron-deficient aryl halides or electron-rich diarylamines undergo faster rates of reductive elimination. A Hammett study employing SPhos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) and analogues of SPhos demonstrated that electron donation of the lower aryl group is key to the stability of the amido complex with respect to reductive elimination. The rate of reductive elimination of an amido complex based on a BrettPhos-RuPhos hybrid ligand (2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,6′-diisopropoxybiphenyl) demonstrated that the presence of the 3-methoxy substituent on the "upper" ring of the ligand slows the rate of reductive elimination. These studies indicate that reductive elimination occurs readily for more nucleophilic amines such as N-alkyl anilines, N,N-dialkyl amines, and primary aliphatic amines using this class of ligands.