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Perfluorinated oxaziridines: (a) Petrov, V. A.; Resnati, G. Chem. Rev. 1996, 96, 1809-1824.
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Alkoxysulfonyl oxaziridines: (b) Brodsky, B. H.; Du Bois, J. J. Am. Chem. Soc. 2005, 127, 15391-15393.
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Related oxaziridinium salts: (c) Poisson, D.; Cure, G.; Solladié, G.; Hanquet, G. Tetrahedron Lett. 2001, 42, 3745-3748.
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The oxidation of thiolates into sulfenates is not a common reaction in organic synthesis: (a) O'Donnell, J. S.; Schwan, A. L. J. Sulfur Chem. 2004, 25, 183-211.
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The oxidation of thiolates into sulfenates is not a common reaction in organic synthesis: (a) O'Donnell, J. S.; Schwan, A. L. J. Sulfur Chem. 2004, 25, 183-211.
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In contrast, this reaction is more encountered in biology, especially with processes involving cysteine residues: (b) Forman, H. J.; Fukuto, J. M.; Torres, M. Am. J. Physiol. Cell. Physiol. 2004, 287, C246-C256.
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In contrast, this reaction is more encountered in biology, especially with processes involving cysteine residues: (b) Forman, H. J.; Fukuto, J. M.; Torres, M. Am. J. Physiol. Cell. Physiol. 2004, 287, C246-C256.
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(a) Sandrinelli, F.; Perrio, S.; Beslin, P. J. Org. Chem. 1997, 62, 8626-8627.
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Alternative routes to sulfenate species consist of manipulation of sulfoxides possessing an appropriate functionality, the most relevant contributions being the oxidative cleavage of 1-alkynyl sulfoxides with a Pd(0)-catalyst followed by transmetalation with Et2Zn, an addition/elimination methodology with β-sulfinylacrylates, a retro-Michael reaction initiated by a base from β-sulfinyl esters, and finally, the fluoride-mediated deprotection of 2-(trimethylsilyl)ethyl sulfoxides. See ref 5a and: (a) Caupène, C, Boudou, C, Perrio, S, Metzner, P. J. Org. Chem. 2005, 70, 2812-2815
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2Zn, an addition/elimination methodology with β-sulfinylacrylates, a retro-Michael reaction initiated by a base from β-sulfinyl esters, and finally, the fluoride-mediated deprotection of 2-(trimethylsilyl)ethyl sulfoxides. See ref 5a and: (a) Caupène, C.; Boudou, C.; Perrio, S.; Metzner, P. J. Org. Chem. 2005, 70, 2812-2815.
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We previously reported that the outcome of the oxidation reaction with aromatic thiolates highly depends on the oxaziridine structure: Sandrinelli, F, Perrio, S, Beslin, P. Org. Lett. 1999, 1, 1177-1180
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We previously reported that the outcome of the oxidation reaction with aromatic thiolates highly depends on the oxaziridine structure: Sandrinelli, F.; Perrio, S.; Beslin, P. Org. Lett. 1999, 1, 1177-1180.
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0001414645
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Sulfenate salts, whose structure contains an unshared electron pair adjacent to the sulfur center, are considered as α-nucleophiles with an exalted reactivity. As a direct consequence, the double oxidation reaction leading to the sulfinate is generally preferred: Kice, J. L.; Cleveland, J. P. J. Am. Chem. Soc. 1973, 95, 104-109.
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Sulfenate salts, whose structure contains an unshared electron pair adjacent to the sulfur center, are considered as α-nucleophiles with an exalted reactivity. As a direct consequence, the double oxidation reaction leading to the sulfinate is generally preferred: Kice, J. L.; Cleveland, J. P. J. Am. Chem. Soc. 1973, 95, 104-109.
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The reaction of this type of reagent with lithium and Grignard reagent, lithium amide bases and potassium phenolates, proceeds probably with an initial electron-transfer mechanism: (c) Davis, F. A.; Mancinelli, P. A.; Balasubramanian, K.; Nadir, U. K. J. Am. Chem. Soc. 1979, 101, 1044-1045.
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The reaction of this type of reagent with lithium and Grignard reagent, lithium amide bases and potassium phenolates, proceeds probably with an initial electron-transfer mechanism: (c) Davis, F. A.; Mancinelli, P. A.; Balasubramanian, K.; Nadir, U. K. J. Am. Chem. Soc. 1979, 101, 1044-1045.
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A single isomer, probably with an E configuration, is obtained: (a) Lipshutz, B. H.; Shimizu, H. Angew. Chem., Int. Ed. Engl. 2004, 43, 2228-2230.
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This is particularly the case with those with α-enolizable protons: (a) Desrosiers, J.-N.; Côté, A.; Charette, A. B. Tetrahedron 2005, 61, 6186-6192.
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34447335475
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1H NMR spectroscopy. As a single equivalent of oxidant was employed, sulfinate formation implied systematically the presence of unreacted thiolate, which upon the electrophilic quench was readily converted in situ into the corresponding thioether.
-
1H NMR spectroscopy. As a single equivalent of oxidant was employed, sulfinate formation implied systematically the presence of unreacted thiolate, which upon the electrophilic quench was readily converted in situ into the corresponding thioether.
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0020765317
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When an excess of n-BuLi was introduced, benzylated imine 6 was detected. Its formation was interpreted by hydrogen abstraction on the methyl substituent of the liberated imine 4b, followed by C-alkylation of the resulting azaallyl anion. As a checking experiment, direct reaction with 4b in the presence of a stoichiometric amount of base furnished 6 in 40% yield. For precedents with other imines, see: (a) Smith, J. K.; Bergbreiter, D. E.; Newcomb, M. J. Am. Chem. Soc. 1983, 105, 4396-4400.
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When an excess of n-BuLi was introduced, benzylated imine 6 was detected. Its formation was interpreted by hydrogen abstraction on the methyl substituent of the liberated imine 4b, followed by C-alkylation of the resulting azaallyl anion. As a checking experiment, direct reaction with 4b in the presence of a stoichiometric amount of base furnished 6 in 40% yield. For precedents with other imines, see: (a) Smith, J. K.; Bergbreiter, D. E.; Newcomb, M. J. Am. Chem. Soc. 1983, 105, 4396-4400.
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37049137779
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Aldimines 4d-e were produced completely in the E configuration: (a) Bjørgo, J.; Boyd, D. R.; Watson, C. G.; Jennings, W. B.; Jerina, D. M. J. Chem. Soc., Perkin Trans. 2 1974, 1081-1084.
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