- Electrochemical synthesis of sulfinic esters from alcohols and thiophenols
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Electrochemical oxidative couplings between S[sbnd]H and O[sbnd]H bonds are achieved herein directly from readily-available alcohols and thiophenols, affording a series of diverse sulfinic esters. This strategy can take advantage of 6 equivalents of alcohol, relative to thiophenol, to achieve moderate to good yields, without the assistance of any metallic catalysts, bases, and additional oxidants.
- He, Yang,Zhang, Jinli,Xu, Liang,Wei, Yu
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supporting information
(2020/01/31)
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- Copper-Catalyzed Multicomponent Reaction of DABCO·(SO2)2, Alcohols, and Aryl Diazoniums for the Synthesis of Sulfonic Esters
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A Cu-catalyzed multicomponent cascade reaction of DABCO·(SO2)2 (DABSO), alcohol, and aryl diazonium tetrafluoroborate was developed which afforded sulfonic esters in moderate to good chemical yields. In this reaction, the SO2 surrogate DABSO was used for the first time in the synthesis of sulfonic aliphatic esters. This multicomponent reaction was carried out under mild conditions and tolerated a wide range of substrates, which provides a new and efficient strategy for the synthesis of sulfonic esters.
- Wang, Yang,Deng, Lingling,Deng, Yu,Han, Jianlin
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p. 4674 - 4680
(2018/04/26)
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- Photoinduced Oxidative Cross-Coupling for O-S Bond Formation: A Facile Synthesis of Alkyl Benzenesulfonates
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We have developed a photoinduced oxidative cross-coupling of thiophenols with alcohols for O-S bond formation. The protocol uses visible light, a metal-free photocatalyst, and oxygen as the oxidant for the selective synthesis of alkyl benzenesulfonates; no ligand co-additive is necessary. Mechanistic studies suggested that the disulfide and alkyl benzenesulfinate are involved as intermediates and that the transformation proceeds by a radical pathway.
- Singh, Atul K.,Yi, Hong,Zhang, Guoting,Bian, Changliang,Pei, Pengkun,Lei, Aiwen
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supporting information
p. 1558 - 1563
(2017/08/11)
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- Hammett Correlations in the Photosensitized Oxidation of 4-Substituted Thioanisoles
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Singlet oxygen is quenched by a series of 4-substituted thioanisoles (methoxy to nitro), with rate constant kt = 7 × 104 to 7 × 106 M-1 s-1, close to the value observed for the myoglobin-catalyzed sulfoxidation of the same sulfides. Correlations with σ (ρ = -1.97) and with Eox (slope -3.9 V-1) are evidence for an electrophilic mechanism. In methanol sulfoxides are formed (85%) via an intermediate quenched by diphenyl sulfoxide; competing minor paths lead to arylthiols, arylsulfenic acid, and aryl sulfoxides. In aprotic solvents, the sulfoxidation is quite sluggish, but carboxylic acids (mostly ≤0.1 M) enhance the rate by a factor of > 100. The protonated persulfoxide is formed in this case and acts as an electrophile with sulfides, again with a rate constant correlating with σ (ρ = -1.78).
- Bonesi, Sergio M.,Fagnoni, Maurizio,Albini, Angelo
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p. 928 - 935
(2007/10/03)
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- The Hammett equation and micellar effects on SN2 reactions of methyl benzenesulfonates - The role of micellar polarity
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Substituent effects on the reaction of H2O, OH-, and Br- with p-substituted methyl benzenesulfonates in cationic micelles of cetyl trialkylammonium ion surfactants (n-C16H33NR3X, X = OH, Br, R = Me, Et, nPr, nBu) and in water were analyzed by using the Hammett equation. Values of p in the various media confirm that micellar interfacial regions are less polar than water and polarities decrease with increasing bulk of the surfactant head-group. Wiley-VCH Verlag GmbH, 2000.
- Brinchi, Lucia,Di Profio, Pietro,Germani, Raimondo,Savelli, Gianfranco,Spreti, Nicoletta,Bunton, Clifford A.
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p. 3849 - 3854
(2007/10/03)
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- Limitations of the Transition-state Variation Model. Part 3. Solvolyses of Electron-rich Benzenesulphonyl Chlorides
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Rate constants for solvolyses of 4-methoxy-2,6-dimethylbenzenesulphonyl chloride 3 (Z = OMe) and of 4-methyl- and 4-methoxybenzenesulphonyl chlorides 4 (Z = Me and OMe) are reported for aqueous binary mixtures with acetone, ethanol and methanol.Some additional rate constants are reported for aqueous acetonitrile and dioxane mixtures, as well as product selectivities (S) in alcohol-water mixtures.For each binary mixture, rates of solvolyses of 3 (Z = OMe) vs.YCl or Y are approximately bilinear.As water is added to alcohol, S values for solvolyses of 3 (Z = OMe) pass through a maximum and for solvolyses of 4-methoxybenzenesulphonyl chloride 4 (Z = OMe) the position of the maximum shifts to more aqueous media.For solvolyses of 4-methyl-benzenesulphonyl chloride 4 (Z = Me), S values are shifted such that they reach a plateau rather than a maximum, and the rate-rate profiles with YCl are approximately linear rather than bilinear.All of rate-rate profiles show 'dispersion' into separate correlations for the various binary mixtures.These substituent effects follow the same trends as corresponding solvolyses of benzoyl chloride and strengthen recent proposals that solvolyses of 3 (Z = Me) proceed via competing (dual) reaction channels.
- Koo, In Sun,Bentley, William T.,Llewellyn, Gareth,Yang, Kiyull
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p. 1175 - 1179
(2007/10/02)
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- Methyl Transfers. 8. The Marcus Equation and Transfer between Arenesulfonates
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Using a 35S label, rates of identity methyl-transfer reactions XC6H4*SO3(1-) + CH3O3SC6H4X -> XC6H4*SO3CH3 + XC6H4SO3(1-) in sulfolane have been measured.For all five cases, these identity rates fit the Hammett equation with the rather large ρ of +0.6.Rates and equilibria for XC6H5SO3Me + 3,4-Cl2C6H3SO3(1-) have been measured.The fit to the Marcus equation using averages of the experimental identity rates for the intrinsic rate is perfect, within experimental error.The absolute values of ρ for the forward and reverse reactions differ by an amount quantitatively consistent with the nonzero identity reaction ρ.The significance of the identity reaction ρ > 0 is discussed.
- Lewis, Edward S.,Hu, Daniel D.
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p. 3292 - 3296
(2007/10/02)
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- Perchlorate Esters. Part 3. Correlation of the Rates of Reaction of Arenesulphonate Ions with Methyl Perchlorate in Acetonitrile
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Second-order rate coefficients for the reactions of acetonitrile solutions of tetra-n-butylammonium benzensulphonate and seven meta- and para-substituted derivatives with methyl perchlorate, at 0.3 deg C lead to a Hammet ρ value (-1.10 +/- 0.04) essentially identical to those previously reported for reactions with other powerful methylating agents.When silver ion is substituted for tetra-n-butylammonium ion, the second-oreder rate coefficients become concetration dependent and the fall of with increasing salt concetration can be rationalised on the basis of only free anions being reactive.The calculated degrees of dissociation are applied tothe previously studied silver0ion assisted reaction of silver toluene-p-sulphonate with methyl iodide.
- Kevill, Dennis N.,Lin, Gloria Meichia L.,Bahari, Mohd S.
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- CORRELATION OF THE RATES OF REACTION OF ARENESULFONATE IONS WITH THE TRIMETHYLOXONIUM ION IN ACETONITRILE
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The kinetics of the reactions between trimethyloxonium hexafluorophosphate and a series of tetra-n-butylammonium arenesulfonates have been studied in acetonitrile at -23.4 deg C.With the oxonium salt concentration at about 0.01 M, two series of runs were carried out; Hammett plots of the second-order rate coefficients led to ρ values of -1.18 +/- 0.04 for 0.04 M arenesulfonate salt and -1.07 +/- 0.02 for 0.16 M arenesulfonate salt.Solvolysis kinetics for the trimethyloxonium ion in acetonitrile are also reported.
- Kevill, Dennis N.,Lin, Gloria Meichia L.,Wang, An
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p. 715 - 717
(2007/10/02)
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