86364-01-4Relevant articles and documents
Palladium-Catalyzed Synthesis of N, N-Dimethylanilines via Buchwald-Hartwig Amination of (Hetero)aryl Triflates
Pospech, Jola,Taeufer, Tobias
, p. 7097 - 7111 (2020/06/27)
This work delineates the synthesis of N,N-dimethylaniline derivatives from dimethylamines and aryl triflates. The palladium-catalyzed C-N bond formation proceeds in excellent yields, using an unsophisticated catalytic system, a mild base, and triflates as electrophiles, which are readily available from inexpensive phenols. N,N-Dimethylanilines are multifunctional reaction partners and represent useful but underutilized building blocks in organic synthesis.
Transition-Metal-Free C-C, C-O, and C-N Cross-Couplings Enabled by Light
Liu, Wenbo,Li, Jianbin,Querard, Pierre,Li, Chao-Jun
supporting information, p. 6755 - 6764 (2019/05/06)
Transition-metal-catalyzed cross-couplings to construct C-C, C-O, and C-N bonds have revolutionized chemical science. Despite great achievements, these metal catalysts also raise certain issues including their high cost, requirement of specialized ligands, sensitivity to air and moisture, and so-called "transition-metal-residue issue". Complementary strategy, which does not rely on the well-established oxidative addition, transmetalation, and reductive elimination mechanistic paradigm, would potentially eliminate all of these metal-related issues. Herein, we show that aryl triflates can be coupled with potassium aryl trifluoroborates, aliphatic alcohols, and nitriles without the assistance of metal catalysts empowered by photoenergy. Control experiments reveal that among all common aryl electrophiles only aryl triflates are competent in these couplings whereas aryl iodides and bromides cannot serve as the coupling partners. DFT calculation reveals that once converted to the aryl radical cation, aryl triflate would be more favorable to ipso substitution. Fluorescence spectroscopy and cyclic voltammetry investigations suggest that the interaction between excited acetone and aryl triflate is essential to these couplings. The results in this report are anticipated to provide new opportunities to perform cross-couplings.
Solvent-free ruthenium-catalysed triflate coupling as a convenient method for selective azole-o-C-H monoarylation
Abidi, Oumaima,Boubaker, Taoufik,Hierso, Jean-Cyrille,Roger, Julien
supporting information, p. 5916 - 5919 (2019/06/24)
Metal-catalysed ortho-directed C-H functionalization usually faces selectivity issues in the competition between mono- and disubstitution processes. We report herein the ruthenium-catalysed N-directed C-H monoarylation of arylpyrazoles with a selectivity
Reaction of Triflates with Potassium Diethyl Phosphite. Formation of Phosphate Esters
Creary, Xavier,Benage, Brigitte,Hilton, Kathryn
, p. 2887 - 2891 (2007/10/02)
Phenyl triflate and substituted analogues react with potassium diethyl phosphite in liquid ammonia to form aryl diethyl phosphate esters.The reaction formally involves loss of trifluoromethanesulfinate ion from the triflate and concomitant oxidation of phosphorus to the phosphate stage.Preliminary data suggest that, in a series of triflates, reactivity follows the order aryl > cyclohexenyl > cyclopropyl > alkyl.Studies on aryl triflates with added labeled phenoxide rule out a mechanism involving free phenoxide ion, i.e., displacement of phenoxide by nucleophilic attack of diethyl phosphite ion on sulfur followed by phosphorylation of displaced phenoxide.Three potential mechanisms, including one involving initial attack of phosphorus at sulfur, a biphilic insertion mechanism, and one involving nucleophilic attack on oxygen, are suggested, all of which could account for these observations.
