3111-54-4Relevant articles and documents
Dimsyl Anion Enables Visible-Light-Promoted Charge Transfer in Cross-Coupling Reactions of Aryl Halides
Pan, Lei,Cooke, Maria Victoria,Spencer, Amara,Laulhé, Sébastien
, p. 420 - 425 (2021/11/01)
A methodology is reported for visible-light-promoted synthesis of unsymmetrical chalcogenides enabled by dimsyl anion in the absence of transition-metals or photoredox catalysts. The cross-coupling reaction between aryl halides and diaryl dichalcogenides proceeds with electron-rich, electron-poor, and heteroaromatic moieties. Mechanistic investigations using UV-Vis spectroscopy, time-dependent density functional theory (TD-DFT) calculations, and control reactions suggest that dimsyl anion forms an electron-donor-acceptor (EDA) complex capable of absorbing blue light, leading to a charge transfer responsible for generation of aryl radicals from aryl halides. This previously unreported mechanistic pathway may be applied to other light-induced transformations performed in DMSO in the presence of bases and aryl halides.
2-Pyridyl Sulfoxide Directed Pd(II)-Catalyzed C-H Olefination of Arenes with Molecular Oxygen as the Sole Oxidant
Yadav, Mamta,Jat, Ram Singh,Sarma, Bibek,Bhanuchandra
, p. 2269 - 2276 (2021/03/03)
Pd(II)-catalyzed C-H olefination of aryl 2-pyridyl sulfoxides with unactivated and activated olefins has been demonstrated. We employed environmentally benign and inexpensive molecular oxygen as the sole oxidant. The versatile nature of the 2-pyridyl sulf
Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation
K?nig, Burkhard,Wang, Hua,Wang, Shun
supporting information, p. 1653 - 1665 (2021/06/17)
Substantial effort is currently being devoted to obtaining photoredox catalysts with high redox power. Yet, it remains challenging to apply the currently established methods to the activation of bonds with high bond dissociation energy and to substrates with high reduction potentials. Herein, we introduce a novel photocatalytic strategy for the activation of inert substituted arenes for aryl borylation by using thiolate as a catalyst. This catalytic system exhibits strong reducing ability and engages non-activated Caryl–F, Caryl–X, Caryl–O, Caryl–N, and Caryl–S bonds in productive radical borylation reactions, thus expanding the available aryl radical precursor scope. Despite its high reducing power, the method has a broad substrate scope and good functional-group tolerance. Spectroscopic investigations and control experiments suggest the formation of a charge-transfer complex as the key step to activate the substrates.