105769-48-0Relevant articles and documents
Phosphine Evaluation on a New Series of Heteroleptic Copper(I) Photocatalysts with dpa Ligand [Cu(dpa)(P,P)]BF4
Henriquez, Marco A.,Engl, Sebastian,Jaque, Pablo,Gonzalez, Ivan A.,Natali, Mirco,Reiser, Oliver,Cabrera, Alan R.
, p. 4020 - 4029 (2021)
Five new heteroleptic copper(I) complexes (C1-5) of the type [Cu(dpa)(P,P)]BF4 based on dipyridylamine (dpa) as N,N ligand and commercial diphosphines as P,P ancillary ligands have been synthesised through a simple methodology with high yields. All complexes were thoroughly characterised by spectroscopic and spectrometric techniques, as well by theoretical calculations. These showed Metal to Ligand Charge Transfer (MLCT) absorptions in the 300–370 nm region, and emission in the 450–520 nm region with quantum yields and lifetimes that depend on the nature of the P,P ligand. The photocatalytic performance of copper(I) complexes C1-5 was evaluated for their use as photoredox catalysts in ATRA reactions, decarboxylative coupling and an Appel-type reaction. The use of readily available dpa as N,N ligand constitutes an attractive alternative to the well-established phenanthroline ligands typically used in photocatalysis.
Atom-transfer radical addition (ATRA) and cyclization (ATRC) reactions catalyzed by a mixture of [RuCl2Cp*(PPh3)] and magnesium
Thommes, Katrin,Icli, Burcak,Scopelliti, Rosario,Severin, Kay
, p. 6899 - 6907 (2007)
A new catalytic procedure for atom-transfer radical addition (ATRA) and cyclization (ATRC) reactions is described. The combination of the ruthenium(III) complex [RuCl2-Cp*(PPh3)] (Cp*: pentamethylcyclopentadienyl) with magnesium allows these reactions to be performed under mild conditions with high efficiency. In most cases, the catalyst concentrations required are significantly lower than those used in previously reported procedures. It is suggested that magnesium acts as a reducing agent that generates and regenerates the catalytically active ruthenium(II) species. The precatalyst [RuCl2Cp*(PPh 3)] has been analyzed by X-ray crystallography.
Copper-Catalyzed Chloro-Arylsulfonylation of Styrene Derivatives via the Insertion of Sulfur Dioxide
Li, Yue,Shen, Lin,Zhou, Mi,Xiong, Baojian,Zhang, Xuemei,Lian, Zhong
, p. 5880 - 5884 (2021)
A copper-catalyzed four-component chloro-arylsulfonylation of styrene derivatives with aryldiazonium tetrafluoroborates, lithium chloride, and ex-situ generated sulfur dioxide (from SOgen) is presented. This sulfonylation features good functional group compatibility, mild reaction conditions, excellent regioselectivity, and good yields. The robustness and potential of this method have also been successfully demonstrated by a gram-scale reaction. Based on experimental study, a radical-involved mechanism is proposed for the transformation.
An efficient, selective, and reducing agent-free copper catalyst for the atom-transfer radical addition of halo compounds to activated olefins
Munoz-Molina, Jose Maria,Belderrain, Tomas R.,Perez, Pedro J.
, p. 642 - 645 (2010)
Efficient and selective ATRA reactions of CCl4, CBr4, TsCl (Ts = tosyl), or Cl3CCO2Et with activated olefins (styrene, methyl methacrylate, n-butyl methacrylate, ferf-butyl methacrylate) using the TptBuCu(NCMe) complex as a catalyst have been achieved In the absence of any reductant and with low catalyst loadings.
Making Copper Photocatalysis Even More Robust and Economic: Photoredox Catalysis with [CuII(dmp)2Cl]Cl
Engl, Sebastian,Reiser, Oliver
, p. 1523 - 1533 (2020)
The CuII complex [CuII(dmp)2Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) is evaluated as an oxidation stable precursor for visible-light-mediated CuI-photoredox catalysis, being efficient and considerable more cost-effective compared to previously established copper(I) photocatalysts. Its performance and efficiency are demonstrated within a broad scope of atom transfer radical addition (ATRA) reactions, allowing the 1,2-difunctionalization of alkenes, as well as for decarboxylative coupling and an Appel reaction. Moreover, the utility of the complex is shown by various gram-scale functionalizations of styrene, thus suggesting [CuII(dmp)2Cl]Cl to be a low-priced alternative precatalyst for processes run on scale. Furthermore, this study provides UV/Vis evidence on the mechanism for the visible light activation of CuII complexes.
Cu-Catalyzed photoredox chlorosulfonation of alkenes and alkynes
Alkan-Zambada, Murat,Hu, Xile
supporting information, p. 4525 - 4533 (2019/04/25)
Visible-light photoredox chlorosulfonation of alkenes and alkynes is achieved using a Cu photocatalyst. The reactions occur under mild conditions, have broad scope, and have high functional group tolerance.
Visible-Light-Mediated Regioselective Chlorosulfonylation of Alkenes and Alkynes: Introducing the Cu(II) Complex [Cu(dap)Cl2] to Photochemical ATRA Reactions
Hossain, Asik,Engl, Sebastian,Lutsker, Eugen,Reiser, Oliver
, p. 1103 - 1109 (2019/02/10)
A visible-light-mediated photocatalyzed protocol utilizing copper-phenanthroline-based catalysts has been developed that can convert a large number of olefins into their chlorosulfonylated products. Besides the Cu(I) complex [Cu(dap)2]Cl, now well-established in photo-ATRA processes, the corresponding Cu(II) complex [Cu(dap)Cl2] proved to be often even more efficient in the title reaction, being advantageous from an economic point of view but also opening up new avenues for photoredox catalysis. Moreover, the copper complexes outperformed commonly used ruthenium, iridium, or organic dye based photocatalysts, owing to their ability to stabilize or interact with transient radicals by inner sphere mechanisms. The use of stoichiometric Na2CO3 in combination with the copper photocatalysts was found to be essential to convert unactivated olefins to the desired products, in contrast to activated olefins for which no additive was required. As suggested by appropriate control experiments, the role of Na2CO3 is attributed to prevention of poisoning of the catalyst.
Iron(III) Chloride-Mediated Regio- and Stereoselective Chlorosulfonylation of Alkynes and Alkenes with Sodium Sulfinates
Zeng, Kui,Chen, Lang,Chen, Yi,Liu, Yongping,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
supporting information, p. 841 - 847 (2017/03/11)
The atom-economic and one-pot regio- and stereoselective addition of sodium arenesulfinates to either alkynes or alkenes can be achieved with an iron(III) chloride hexahydrate [FeCl3?6 H2O] catalytic system to afford β-haloalkenyl and β-chloroalkyl sulfones in moderate to good yields. (Figure presented.).
Visible light-mediated atom transfer radical addition via oxidative and reductive quenching of photocatalysts
Wallentin, Carl-Johan,Nguyen, John D.,Finkbeiner, Peter,Stephenson, Corey R. J.
supporting information; experimental part, p. 8875 - 8884 (2012/07/02)
Herein, the development of visible light-mediated atom transfer radical addition (ATRA) of haloalkanes onto alkenes and alkynes using the reductive and oxidative quenching of [Ir{dF(CF3)ppy}2(dtbbpy)]PF 6 and [Ru(bpy)3]Cl2 is presented. Initial investigations indicated that the oxidative quenching of photocatalysts could effectively be utilized for ATRA, and since that report, the protocol has been expanded by broadening the scope of the reaction in terms of the photocatalysts, substrates, and solvents. In addition, further modifications of the reaction conditions allowed for the efficient ATRA of perfluoroalkyl iodides onto alkenes and alkynes utilizing the reductive quenching cycle of [Ru(bpy) 3]Cl2 with sodium ascorbate as the sacrificial electron donor. These results signify the complementary nature of the oxidative and reductive quenching pathways of photocatalysts and the ability to predictably direct reaction outcome through modification of the reaction conditions.
Modulating the steric, electronic, and catalytic properties of Cp* ruthenium half-sandwich complexes with β-diketiminato ligands
Phillips, Andrew D.,Thommes, Katrin,Scopelliti, Rosario,Gandolfi, Claudio,Albrecht, Martin,Severin, Kay,Schreiber, Dominique F.,Dyson, Paul J.
experimental part, p. 6119 - 6132 (2012/01/04)
Five different types of β-diketiminate ligands, bearing electron-donating to strongly electron-withdrawing substituents, were synthesized and used in the synthesis of Cp* ruthenium complexes (Cp* = η5-C5Me5). One series consists of complexes with a covalent RuIII-Cl bond, and the other series features a reduced RuII center, where the chloride is abstracted by treatment of the corresponding RuIII compounds with Zn or Mg. All compounds were characterized by single-crystal X-ray diffraction, UV-visible spectroscopy, and cyclic voltammetry. In the case of RuII complexes, solution NMR techniques provided key information regarding the electronic and structural differences induced by the different β-diketiminate ligands employed. Capitalizing on the facile reduction-oxidation cycle of the Cp* ruthenium β-diketiminato complexes, catalytic atom transfer radical addition (ATRA) and cyclization (ATRC) reactions were performed on relevant substrates. The turnover rates are strongly dependent on the type of β-diketiminate used, where ligands with electron-withdrawing substituents, i.e., trifluoromethyl groups, provided complexes that efficiently catalyze the addition of CCl4 or toluenesulfonyl chloride to styrene. In contrast, complexes with electron-donating substituents on the β-diketiminate promoted efficient ATR cyclization of N-allyl-N-phenyltrichloroacetamide and 2,2,2-trichloroethyl ether. Thus, the overall product conversion and yield are dependent on matching the ligand substitution pattern of the catalyst to the type of substrate.
