18438-38-5Relevant articles and documents
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.
Carbon-sulfur bond reductive coupling from a platinum(II) thiolate complex
Niazi, Maryam,Shahsavari, Hamid R.,Haghighi, Mohsen Golbon,Halvagar, Mohammad Reza,Hatami, Samaneh,Notash, Behrouz
, p. 95073 - 95084 (2016/10/22)
The room temperature addition of electrophilic alkyl halide reagents (RX = MeI, EtI and PhCH2Br) to complex [Pt(ppy)(η1-S-Spy)(PPh3)], 1a, in which ppyH = 2-phenylpyridine and pySH = pyridine-2-thiol, resulted in a rapid carbon-sulfur (C-S) bond reductive coupling to produce alkyl sulfides and corresponding halide complexes [Pt(ppy)(PPh3)X], X = I (2a) and Br (2b). A mechanism for this C-S bond formation reaction was suggested based on 1H and 31P {1H} NMR spectroscopic analyses. In the suggested mechanism, the reaction proceeded through a binuclear intermediate complex [{Pt(ppy)(PPh3)}2(μ2-Spy)]I, 3-I, which was separately synthesized by another counter anion (PF6) and it was fully characterized by multinuclear NMR spectroscopy and single X-ray crystallography. Also, density functional theory (DFT) calculations were used to theoretically assess the structures of intermediates and transition states in this bond formation reaction.
Nitrogen Transfer to Carbon Radicals
Barton, Derek H.R.,Jaszberenyi, Joseph Cs.,Theodorakis, Emmanouil A.
, p. 5904 - 5905 (2007/10/02)
-
