107456-48-4Relevant academic research and scientific papers
Arylation with unsymmetrical diaryliodonium salts: A chemoselectivity study
Malmgren, Joel,Santoro, Stefano,Jalalian, Nazli,Himo, Fahmi,Olofsson, Berit
supporting information, p. 10334 - 10342 (2013/09/02)
Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new "anti-ortho effect" has been identified in the arylation of malonates. Several "dummy groups" have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents. Copyright
Palladium-catalyzed amination of aryl and heteroaryl tosylates at room temperature
Ogata, Tokutaro,Hartwig, John F.
supporting information; experimental part, p. 13848 - 13849 (2009/02/07)
Mild palladium-catalyzed aminations of aryl tosylates and the first aminations of heteroaryl tosylates are described. In the presence of the combination of L2Pd(0) (L = P(o-tol)3) and the hindered Josiphos ligand CyPF-t-Bu, a variety of primary alkylamines and arylamines react with both aryl and heteroaryl tosylates at room temperature to form the corresponding secondary arylamines in high yields with complete selectivity for the monoarylamine. These reactions at room temperature occur in many cases with catalyst loadings of 0.1 mol % and 0.01 mol % in one case, constituting the most efficient aminations of aryl tosylates by nearly 2 orders of magnitude. This catalyst is made practical by the development of a convenient method to synthesize the L2Pd(0) precursor. This complex is stable to air as a solid. In contrast to conventional relative rates for reactions of aryl sulfonates, the reactions of aryl tosylates are faster than parallel reactions of aryl triflates, and the reactions of aryl tosylates are faster than parallel or competitive reactions of aryl chlorides. Copyright
Aryllead Triacetates: Regioselective Reagents for N-Arylation of Amines
Barton, Derek H. R.,Donnelly, Dervilla, M. X.,Finet, Jean-Pierre,Guiry, Patrick J.
, p. 2095 - 2102 (2007/10/02)
Aryllead triacetates have been found to be regioselective reagents for the mono N-arylation of a range of aromatic, heterocyclic and aliphatic amines under mild and neutral conditions in a reaction catalysed by copper diacetate.The arylation of arylamines was unaffected by the steric hindrance of the arylamine but was dependent on the arylamine basicity.In addition, the position of oxidisable substituents on both the aryllead triacetate and the arylamine was found to be important due to a competing oxidation-reduction reaction.The arylation of heterocyclic amines proceeded in modest to good yields whilst aliphatic amines were arylated in poor to modest yields.The mechanism proposed for these reactions involves transfer of the aryl group onto copper forming a copper(III) intermediate which subsequently undergoes ligand coupling to give the N-arylated amine and the catalytic CuI species.
