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• W2004394441 abstract "Singlet oxygen reacts with thietane, 1, to give the sulfoxide, 1S0, and a trace of sulfone, 1SOz. A mechanism which involves a novel substrate catalyzed interconversion of a persulfoxide and thiadioxirane intermediate is proposed. The data which support the reaction of the persulfoxide with 1 by attack at sulfonium sulfur include the facts that Ph2SO and 1 compete for a common intermediate and physical quenching is suppressed by increasing concentrations of 1. The unique ability of 1 to catalyze its own oxidation is a result of a small C-S-C angle which allows an unencumbered approach to the sulfonium sulfur. In contrast, the larger C-S-C angle in Et2S sterically precludes the catalysis step and forces direct collapse of the persulfoxide to the thiadioxirane intermediate. In 1983, 30 years after the first report of the photooxidation of a dialkyl sulfide,‘ Foote and co-workers2 suggested a mechanism for the reaction of singlet oxygen (‘02) with diethyl sulfide (Et2S) which has served as the prototypical example for sulfide photooxidation reaction surfaces. The unique feature of the Foote mechanism was the suggestion of two intermediates, a persulfoxide which collapsed to the second intermediate in competition with physical quenching, and a thiadioxirane which reacts with a molecule of substrate to give the sulfoxide product. Recently, however, concerns about the viability of the second intermediate on the Foote reaction surface have called into question the generality of this mechanism and have pointed out the need for more detailed kinetic studies with other dialkyl sulfide^.^,^ We report here the first extensive study of the photooxidation of a cyclic sulfide, thietane 1, and compare it to the photooxidation of Et& We also suggest a new mechanism for the photooxidation of 1 which differs from the Foote mechanism for Et2S in that it invokes a novel substratecatalyzed interconversion of persulfoxide 2, and thiadioxirane 4, intermediates. Photooxidations of 1 (0.05-0.2 M) in oxygen-saturated CDC13 solutions containing (2-4) x M TPP (tetraphenylporphyrin) as sensitizer were conducted at room temperature by irradiation with a 650-W tungsten-halogen or a 450-W medium-pressure Hg lamp through a 1-cm NaN02 filter solution. Under these carefully controlled conditions the sulfoxide, 1S0, and a trace of the sulfone, lSOz, were the only products observed at either high or low conversion^.^ Identical results were also obtained in benzene and in acetone-d6 at both room and low temperatures. The experimental evidence which supports the mechanism for this photooxidation as outlined in Scheme 1 includes the following: (1) Cophotooxidations of 1 with diphenyl sulfoxide (Ph2SO) and diphenyl sulfide (Ph2S) produce diphenyl sulfone (Ph2SO2) and Ph2S0, respectively. Control reactions demonstrate that Ph2SO and Ph2S are inert to singlet oxygen under the reaction (1) Schenck, G. 0.; Krausch, C. H. Angew. Chem. 1962, 74, 510. (2)Liang, J.-J.; Gu, C.-L.; Kacher, M. L.; Foote, C. S. J. Am. Chem. (3) Watanabe. Y.: Kuriki. N.: Ishicuro. K.: Sawaki. Y . J. Am. Chem. SOC. 1983, 105, 4717-4721. ‘2 SOC. 1991, 113, 2677-2682. (4) Jensen, F. J. Org. Chem. 1992, 57, 6478-6487. 0002-7863/95/1517-9800$09.00/0 Scheme 1" @default.
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• W2004394441 date "1995-10-01" @default.
• W2004394441 modified "2023-09-26" @default.
• W2004394441 title "Reaction of Singlet Oxygen with Thietane. A Novel Example of a Self-Catalyzed Reaction Which Provides Evidence for a Thiadioxirane Intermediate" @default.
• W2004394441 doi "https://doi.org/10.1021/ja00144a003" @default.
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