A Non-Radical Chain Mechanism for Oxygen Atom Transfer with a Thiorhenium(V) Catalyst

2003 ◽  
Vol 42 (25) ◽  
pp. 8122-8124 ◽  
Author(s):  
Katalin Ösz ◽  
James H. Espenson
Keyword(s):  
Oxygen Atom ◽  
Atom Transfer ◽  
Chain Mechanism ◽  
Oxygen Atom Transfer ◽  
Radical Chain ◽  
Radical Chain Mechanism

scholarly journals Stereoselective cobalt-catalyzed halofluoroalkylation of alkynes

2018 ◽  
Vol 9 (7) ◽  
pp. 1795-1802 ◽  
Author(s):  
Guojiao Wu ◽  
Axel Jacobi von Wangelin
Keyword(s):  
Halogen Atom ◽  
Atom Transfer ◽  
Chain Mechanism ◽  
Atom Economy ◽  
Unsaturated Hydrocarbons ◽  
Radical Chain ◽  
Mild Conditions ◽  
Radical Chain Mechanism ◽  
Acetone Water ◽  
Rapid Generation

Stereoselective additions of functionalized reagents to unsaturated hydrocarbons are attractive due to the high atom economy, modularity and rapid generation of complexity. We report a stereoselective cobalt-catalyzed (E)-halofluoroalkylation of alkynes/alkenes that under mild conditions (2 mol% cat., 20 °C, acetone/water, 3 h). This reaction operates via a radical chain mechanism involving terminal halogen atom transfer which obviates the need for a stoichiometric sacrificial reductant.

Oxidation of organic sulphides - II. Interaction of cyclo hexyl methyl sulphide with hydroperoxides in hydrocarbons

1954 ◽  
Vol 224 (1158) ◽  
pp. 399-411 ◽  
Keyword(s):  
Acetic Acid ◽  
Free Radical ◽  
Oxygen Atom ◽  
Transfer Process ◽  
Hydrogen Transfer ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
Radical Chain ◽  
Reaction Orders ◽  
To Come

Oxidations of cyclo hexyl methyl sulphide by cyclo hexenyl and t -butyl hydroperoxides in hydrocarbon solvents simulate those in alcohols (part I) in that the sulphoxide yield is quantitative under all the conditions studied. They differ, however, in their kinetic characteristics, and the complexities of the hydrocarbon systems are found to vary remarkably with the hydroperoxide and with the solvent. The reaction with cyclo hexenyl hydroperoxide in benzene or cyclo hexane is insensitive to the presence of oxygen, evidences no free radical character, and has orders of one with respect to sulphide and two with respect to hydroperoxide. Acetic acid catalyzes the reaction and changes the hydroperoxide order from 2 to 1. Essentially the same oxygen atom transfer process as postulated in alcohols is believed to occur: in the absence of acid, the oxidant is a bimolecular hydroperoxide complex; in the presence of acid, the component molecule effecting the associated hydrogen transfer is displaced by an acid molecule which can per­form this function more efficiently. The reaction with t -butyl hydroperoxide in benzene proceeds faster in air than in a vacuum; the oxygen catalysis is less in cyclo hexane and absent in cyclo hexene. The reaction stoicheiometry remains the same in all cases. The addition of acetic acid, which catalyzes the reaction as indicated for cyclo hexenyl hydroperoxide, completely eliminates the sensitivity to oxygen. Considering oxygen-free systems, the reaction orders with respect to the sulphide are 0∙7 in benzene, 0∙4 in cyclo hexane, and 0∙45 in cyclo hexene; the order with respect to hydroper­oxide is 2 throughout. The reactions are insensitive to free radical inhibitors. It is suggested that oxidation occurs by two concurrent mechanisms; one is the oxygen-atom transfer process referred to above; the other is formulated as a two-stage process involving a hydroperoxide-solvent complex as oxidant, the rate of complex formation being rate-determining. In benzene in the presence of oxygen, the sulphide order is higher (0∙9) and the hydro­peroxide order lower (1∙4); free radical inhibitors effectively repress oxygen catalysis. A free radical chain mechanism therefore appears to come into play in the presence of oxygen, and the postulated requirements of this to account for the unaltered stoicheiometry and the solvent effects are discussed.

scholarly journals Oxygen Atom Transfer Catalysis by Dioxidomolybdenum(VI) Complexes of Pyridyl Aminophenolate Ligands

Polyhedron ◽  
2021 ◽  
pp. 115234
Author(s):  
Md. Kamal Hossain ◽  
Jörg A. Schachner ◽  
Matti Haukka ◽  
Michael G. Richmond ◽  
Nadia C. Mösch-Zanetti ◽  
...  
Keyword(s):  
Oxygen Atom ◽  
Atom Transfer ◽  
Oxygen Atom Transfer

Nonclassical oxygen atom transfer reactions of an eight-coordinate dioxomolybdenum(vi) complex

2021 ◽  
Author(s):  
Leila G. Ranis ◽  
Jacqueline Gianino ◽  
Justin M. Hoffman ◽  
Seth N. Brown
Keyword(s):  
Oxygen Atom ◽  
Transfer Reaction ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
Oxygen Atom Transfer Reactions ◽  
Atom Transfer Reactions ◽  
Oxygen Atoms

Eight-coordinate MoO2(DOPOQ)2 can donate two oxygen atoms to substrates such as phosphines in a four-electron nonclassical oxygen atom transfer reaction.

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