620-93-9Relevant articles and documents
Studies on the amination of aryl chlorides with a monoligated palladium catalyst: Kinetic evidence for a cooperative mechanism
Jimeno, Ciril,Christmann, Ute,Escudero-Adan, Eduardo C.,Vilar, Ramon,Pericas, Miquel A.
, p. 16510 - 16516 (2012)
Combined spectroscopic, crystallographic, and kinetic studies of the mechanism of aromatic amination with the efficient dinuclear Pd precatalyst [Pd2Cl(μ-Cl)PtBu2(Bph-Me)] (Bph-Me=2′-methyl-[1, 1'-biphenyl]-2-yl) have revealed overlapping, yet cooperative, mechanistic scenarios, the relative weights of which are strongly influenced by the products formed as the reaction proceeds. The stability and evolution of the precatalyst in solution has been studied and several metalation pathways that point to a single monoligated intermediate have been identified. Our work sheds light on the nature of the catalytic species involved in the process and on the structure of the corresponding catalytic network. Two cycles for catalytic amination: Combined spectroscopic, crystallographic, and kinetic studies on the amination of p-chlorotoluene with p-toluidine with a monoligated Pd catalyst have revealed overlapping, yet cooperative, mechanistic scenarios, the relative weights of which are strongly influenced by the products formed as the reaction proceeds (see scheme; L=2′-methyl-[1,1'-biphenyl]-2-yl).
Mechanochemical synthesis of aromatic sulfonamides
Iaroshenko, Viktor O.,Mkrtchyan, Satenik
, p. 11029 - 11032 (2021/11/03)
A three-component Pd-catalysed aminosulfonylation reaction of K2S2O5 and amine with aryl bromides or aromatic carboxylic acids was developed. This strategy was developed to utilise mechanical energy and accommodate primary as well as secondary aliphatic and aromatic amines to provide a new shortcut to a wide range of sulfonamides. Studies on the scope and limitations of the reaction indicated its tolerance of a vast range of functional groups and many structural patterns. The reactions were scaled up to gram quantities.
Improved Buchwald-Hartwig Amination by the Use of Lipids and Lipid Impurities
Bayer, Annette,Gevorgyan, Ashot,Hopmann, Kathrin H.
supporting information, (2021/11/12)
The development of green Buchwald-Hartwig aminations has long been considered challenging, due to the high sensitivity of the reaction to the environment. Here we show that food-grade and waste vegetable oils, triglycerides originating from animals, and natural waxes can serve as excellent green solvents for Buchwald-Hartwig amination. We further demonstrate that amphiphiles and trace ingredients present in triglycerides as additives have a decisive effect on the yields of Buchwald-Hartwig aminations.
Electron Push-Pull Effects on Intramolecular Charge Transfer in Perylene-Based Donor-Acceptor Compounds
Ahn, Mina,Kim, Min-Ji,Cho, Dae Won,Wee, Kyung-Ryang
, p. 403 - 413 (2020/12/23)
A series of asymmetric donor-acceptor (D-A) perylene-based compounds, 3-(N,N-bis(4′-(R)-phenyl)amino)perylene (Peri-DPA(R)), were successfully prepared to explore their intramolecular charge transfer (ICT) properties. To induce ICT between the donor and acceptor, diphenylamine (DPA) derivatives (electron donor units) with the same functional groups (R = CN, F, H, Me, or OMe) at both para positions were linked to the C-3 position of perylene to produce five Peri-DPA derivatives. A steady-state spectroscopy study on Peri-DPA(R)s exhibited a progressively regulated ICT trend consistent with the substituent effect as it progressed from the electron-withdrawing group to the electron-donating group. In particular, a comparative study using a D-A-D (donor-acceptor-donor) system demonstrated that not only the electron push-pull substituent effect but also subunit combinations influence photophysical and electrochemical properties. The different ICT characters observed in Lippert-Mataga plots of D-A(CN) and D-A-D(CN) (CN-substituted D-A and D-A-D) led to the investigation on whether ICT emission of two systems with differences in subunit combinations is of the same type or of a different type. The femtosecond transient absorption (fs-TA) spectroscopic results provided direct evidence of ICT origin and confirmed that D-A(CN) and D-A-D(CN) exhibited the same transition mix of ICT (from donor to acceptor) and reverse ICT (rICT, from arylamine to CN unit). Density functional theory (DFT)/TD-DFT calculations support the presence of ICT for all five compounds, and the experimental observations of rICT presented only for CN-substituted compounds.