46181-30-0Relevant articles and documents
C-H and O2Activation at a Pt(II) Center enabled by a novel sulfonated CNN pincer ligand
Watts, David,Wang, Daoyong,Adelberg, Mackenzie,Zavalij, Peter Y.,Vedernikov, Andrei N.
, p. 207 - 219 (2017)
A novel sulfonated CNN pincer ligand has been designed to support CH and O2 activation at a Pt(II) center. The derived cycloplatinated aqua complex 7 was found to be one of the most active reported homogeneous Pt catalysts for H/D exchange between studied arenes (benzene, benzene-d6, toluene-d8, p-xylene, and mesitylene) and 2,2,2-trifluoroethanol (TFE) or 2,2,2- trifluoroethanol-d; the TON for C6D6 as a substrate is >250 after 48 h at 80 °C. The reaction is very selective; no benzylic CH bond activation was observed. The per-CH-bond reactivity diminishes in the series benzene (19) > toluene (p-CH:m-CH:o-CH = 1:0.9:0.2) > xylene (2.9) > mesitylene (1.1). The complex 7 reacts slowly in TFE solutions under ambient light but not in the dark with O2 to selectively produce a Pt(IV) trifluoroethoxo derivative. The H/D exchange reaction kinetics and results of the DFT study suggest that complex 7, and not its TFE derivatives, is the major species responsible for the arene CH bond activation. The reaction deuterium kinetic isotope effect, kH/kD = 1.7, the reaction selectivity, and reaction kinetics modeling suggest that the CH bond cleavage step is rate-determining.
Bathocuproine-Enabled Nickel-Catalyzed Selective Ullmann Cross-Coupling of Two sp 2-Hybridized Organohalides
Li, Yuqiang,Yin, Guoyin
supporting information, p. 1657 - 1661 (2021/09/13)
Cross-coupling reactions are essential for the synthesis of complex organic molecules. Here, we report a nickel-catalyzed Ullmann cross-coupling of two sp 2-hybridized organohalides, featuring high cross-selectivity when the two coupling partners are used in a 1:1 ratio. The high chemoselectivity is governed by the bathocuproine ligand. Moreover, the mild reductive reaction conditions allow that a wide range of functional groups are compatible in this Ullmann cross-coupling.
Meta-dehydrogenative alkylation of arenes with ethers, ketones, and esters catalyzed by ruthenium
Li, Gang,Gao, Yuan,Jia, Chunqi,Wang, Shichong,Yan, Bingxu,Fang, Yu,Yang, Suling
supporting information, p. 8758 - 8763 (2020/12/02)
A meta-dehydrogenative alkylation of arenes with cyclic ethers, ketones, and esters catalyzed by ruthenium is achieved in the presence of a di-tert-butyl peroxide (DTBP) oxidant. Interestingly, when quinoline and isoquinoline are employed as the directing group, or a chain ether as alkylation reagent, the system produces Minisci reaction products. Mechanistic study indicates that meta-dehydrogenative alkylation is a radical process initiated by DTBP with the assistance of a CAr-Ru bond ortho/para-directing effect.