19598-01-7Relevant articles and documents
Electro-mediated PhotoRedox Catalysis for Selective C(sp3)–O Cleavages of Phosphinated Alcohols to Carbanions
Tian, Xianhai,Karl, Tobias A.,Reiter, Sebastian,Yakubov, Shahboz,de Vivie-Riedle, Regina,K?nig, Burkhard,Barham, Joshua P.
supporting information, p. 20817 - 20825 (2021/08/18)
We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp3)?O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp3)?O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions.
Addition of halide to π-bond directly from aqueous NaX solution: A general strategy for installation of two different functional groups
Pandit, Palash,Gayen, Krishnanka S.,Khamarui, Saikat,Chatterjee, Nirbhik,Maiti, Dilip K.
supporting information; experimental part, p. 6933 - 6935 (2011/08/06)
Activation of π-bond with organic Lewis acid and cationic surfactant mediated direct transfer of halides to alkyne and alkene are demonstrated to afford α,α-dihaloketones and other valuable synthons with outstanding selectivities.
Chlorine Dioxide as an Electron-Transfer Oxidant of Olefins
Rav-Acha, Chaim,Choshen, Ehud,Sarel, Shalom
, p. 1728 - 1733 (2007/10/02)
The kinetics and product studies of oxidation of eight olefins 1-8 by ClO2 in H2O in the pH range 3-7 are described.The reaction is faster as the pH decreases.At pH The order of reactivity is: (E)-stilbene > indene > β-methylstyrene > acenaphthylene > α-methylstyrene > styrene > cyclohexene > allylbenzene.A multi-stage radical-cation mechanism is proposed, in which an initial reversible protonation: is followed by an electron-transfer stage (rate-determining): The cation-radical thus produced, adds rapidly an additional ClO2 to from dioxygenated products.The chlorohydrines most likely arise from HClO additions to the olefinic double bonds, which, in turn, generate from dismutation of 2HClO2 into HClO + H+ + ClO3-.