6461-58-1Relevant academic research and scientific papers
Making Copper Photocatalysis Even More Robust and Economic: Photoredox Catalysis with [CuII(dmp)2Cl]Cl
Engl, Sebastian,Reiser, Oliver
supporting information, p. 1523 - 1533 (2019/07/31)
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.
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.
Cu-Catalyzed photoredox chlorosulfonation of alkenes and alkynes
Alkan-Zambada, Murat,Hu, Xile
, 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.
Dual gold and photoredox catalysis: visible light-mediated intermolecular atom transfer thiosulfonylation of alkenes
Li, Haoyu,Shan, Cuicui,Tung, Chen-Ho,Xu, Zhenghu
, p. 2610 - 2615 (2017/04/06)
Regioselective difunctionalization of alkenes has attracted significant attention from synthetic chemists and has the advantage of introducing diverse functional groups into vicinal carbons of common alkene moieties in a single operation. Herein, we report an unprecedented intermolecular atom transfer thiosulfonylation reaction of alkenes by combining gold catalysis and visible-light photoredox catalysis. A trifluoromethylthio group (SCF3) and other functionalized thio groups together with a sulfonyl group were regioselectively introduced into alkenes in the most atom economical manner. A detailed mechanism study indicated that a synergistic combination of gold catalysis and photoredox catalysis is crucial for this reaction.
Kinetics and Mechanism of Michael Addition of Pyrrolidine and Piperidine to a Polarized Double Bond
Kinastowski, Stefan,Kostecki, Marian
, p. 193 - 203 (2007/10/02)
The kinetics and mechanism of reaction of pyrrolidine and piperidine addition to trans-1-phenyl-2-(benzenesulphonyl)ethene (I) have been examined.The mechanism of addition of amines to compound I has been found to be analogous to that proposed for the reaction of trans-chalcone with amines.The addition of amine to the double bond of compound I takes place in a direct way.In the reaction of addition of amines to the polarized double bond three pathways can be distinguished: dimolecular one with participation of amide ions, dimolecular one with participation of free amine, and trimolecular one.
ADDITION OF SULFONYL CHLORIDES TO OLEFINS IN THE PRESENCE OF CATALYTIC AMOUNTS OF DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II)
Kamigata, Nobumasa,Sawada, Hideo,Suzuki, Norihiro,Kobayashi, Michio
, p. 199 - 204 (2007/10/02)
Reactions of sulfonyl chlorides with olefins catalysed by dichlorotris(triphenylphosphine)ruthenium(II) have been studied.Methanesulfonyl and arenesulfonyl chlorides added to 1-alkenes to give 1 : 1 adducts in high yields.Telomer formation is not observed, therefore the present reaction provides a general and convenient method for synthesis of β-chlorosulfones.A radical-chain mechanism is proposed for the reaction.
