13342-30-8Relevant articles and documents
Scope and Limitations of the Pd/BINAP-Catalyzed Amination of Aryl Bromides
Wolfe, John P.,Buchwald, Stephen L.
, p. 1144 - 1157 (2000)
Mixtures of Pd2(dba)3 or Pd(OAc)2 and BINAP catalyze the cross-coupling of amines with a variety of aryl bromides. Primary amines are arylated in high yield, and certain classes of secondary amines are also effectively transformed. The process tolerates the presence of several functional groups including methyl and ethyl esters, enolizable ketones, and nitro groups provided that cesium carbonate is employed as the base. Most reactions proceed to completion with 0.5-1.0 mol % of the palladium catalyst; in some cases, catalyst levels as low as 0.05 mol % Pd may be employed. Reactions are considerably faster if Pd(OAc)2 is employed as the precatalyst, and the order in which reagents are added to the reaction has a substantial effect on reaction rate. It is likely that the catalytic process proceeds via bis(phosphine)palladium complexes as intermediates. These complexes are less prone to undergo undesirable side reactions which lead to diminished yields or catalyst deactivation than complexes of the corresponding monodentate triarylphosphines.
Arenes to anilines and aryl ethers by sequential iridium-catalyzed borylation and copper-catalyzed coupling
Tzschucke, C. Christoph,Murphy, Jaclyn M.,Hartwig, John F.
, p. 761 - 764 (2007/10/03)
(Chemical Equation Presented) N-Alkyl- and N-arylanilines were synthesized from arenes by a two-step sequence of iridium-catalyzed borylation and copper-catalyzed coupling with amines. Diaryl ethers were obtained by a related sequence of arene borylation, followed by coupling with phenols. In particular, 3,5-disubstituted arylamines and aryl ethers were prepared by initiating this sequence with meta-substituted arenes.
