- Practical Electro-Oxidative Sulfonylation of Phenols with Sodium Arenesulfinates Generating Arylsulfonate Esters
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A practical and sustainable synthesis of arylsulfonate esters has been developed through electro-oxidation. This reaction employed the stable and readily available phenols and sodium arenesulfinates as the starting materials and took place under mild reaction conditions without additional oxidants. A wide range of arylsulfonate esters including those bearing functional groups were produced in good to excellent yields. This reaction could also be conducted at a gram scale without a decrease of reaction efficiency. Those results well demonstrated the potential synthetic value of this reaction in organic synthesis.
- Tian, Zhibin,Gong, Qihang,Huang, Tianzeng,Liu, Long,Chen, Tieqiao
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p. 15914 - 15926
(2021/05/04)
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- Electrochemical cross-coupling reactions of sodium arenesulfinates with thiophenols and phenols
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A green electrochemical oxidative cross-coupling protocol for the generation of thiosulfonates and sulfonate esters using sodium arenesulfinates and thiophenols/phenols is disclosed. The protocol involves using inorganic and non-toxic NaI as both redox catalyst and supporting electrolyte at room temperature without oxidant and base. The reactions provide good yields of products and tolerate broad substrate scope. The mechanistic studies revealed that the reactions proceed via a radical pathway for the formation of SO2–S and SO2–O bonds.
- Ma, Jinfeng,Xu, Pan,Zhong, Zijian,Zhou, Aihua
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supporting information
(2021/10/26)
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- NFSI/KF mediated mild and chemoselective interconversion of aryl TBDMS ethers to their benzene sulfonate
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A one pot protocol for the transformation of aryl TBDMS ethers to corresponding benzene sulfonate esters using NFSI (N-flurobenzenesulfonimide)/KF is described. In situ generation of benzenesulfonyl fluoride directs chemoselective cleavage of aryl silyl ethers over alkyl silyl ethers. Electron withdrawing substituent's on aryl ring provided better yield than donating groups. Protecting groups and sensitive functionalities are well tolerated in this methodology. Thus, commercially available inexpensive reagents, mild reaction conditions and step economy are the advantages of this method.
- Dond, Bharat D.,Thore, Shivaji N.
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- Electron Donor-Acceptor Complex Enabled Decarboxylative Sulfonylation of Cinnamic Acids under Visible-Light Irradiation
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Visible-light-induced decarboxylative sulfonylation of cinnamic acids with aryl sulfonate phenol esters enabled by the electron donor-acceptor complex is developed. The method offers a mild and green approach for the synthesis of vinyl sulfones with excellent functional group compatibility under photocatalyst and oxidant-free conditions.
- Ge, Qian-Qian,Qian, Jia-Sheng,Xuan, Jun
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p. 8691 - 8701
(2019/08/30)
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- Iodine-induced synthesis of sulfonate esters from sodium sulfinates and phenols under mild conditions
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An iodine-induced synthesis of sulfonate esters via cross-coupling reactions of sodium sulfinates with phenols is reported. This synthetic route is low-cost, facile, green and efficient, and could afford the target products with good to excellent yields u
- Gao, Jian,Pan, Xiaojun,Liu, Juan,Lai, Junyi,Chang, Liming,Yuan, Gaoqing
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p. 27439 - 27442
(2015/03/31)
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- Kinetic and computational evidence for an intermediate in the hydrolysis of sulfonate esters
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The hydrolytic reactions of sulfonate esters have previously been considered to occur by concerted mechanisms. We now report the observation of a break in a Bronsted correlation for the alkaline hydrolysis of aryl benzenesulfonates. On either side of a break-point, β leaving group values of -0.27 (pKa a > 8.5) are measured. These data are consistent with a two-step mechanism involving a pentavalent intermediate that is also supported by QM/MM calculations. The emerging scenario can be explained by the combined effect of a strong nucleophile with a poor leaving group that compel a usually concerted reaction to favour a stepwise process.
- Babtie, Ann C.,Lima, Marcelo F.,Hollfelder, Florian,Kirby, Anthony J.
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p. 8095 - 8101,7
(2012/12/11)
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- Competitive Reaction Pathways in the Nucleophilic Substitution Reactions of Aryl Benzenesulfonates with Benzylamines in Acetonitrile
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The reactions of aryl benzenesulfonates (YC6H4SO2OC6H4Z) with benzylamines (XC6H4CH2NH2) in acetonitrile at 65.0 deg C have been studied. The reactons proceed competitevely by S-O (kS-O) and C-O (kC-O) bond scission, but the former provides the major reaction pathway. On the basis of analysis of the Hammet and Broensted coefficients together with the cross-interaction constants ρXY, ρYZ, and ρXZ, stepwise mechanisms are proposed in which the S-O bond cleavage proceeds by rate-limiting formation of a trigonal-bipyramidal pentacoordinate (TBP-5C) intermediate, whereas the C-O bond scission takes place by rate-limiting expulsion of the sulfonate anion (YC6H4SO3-) from a Meisenheimer-type complex.
- Choi, Jin Heui,Lee, Byung Choon,Lee, Hai Whang,Lee, Ikchoon
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p. 1277 - 1281
(2007/10/03)
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- The effect of solvent on the α-effect: C=O, P=O and SO2 centers
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The α-effect for the reaction of a sulfonyl ester exhibits a bell-shaped dependence of the α-effect on solvent composition as do the corresponding reactions with a carbonyl and a phosphinyl ester, and the magnitude of the α-effect is found to be dependent
- Um,Hong,Buncel
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- Solvent Independent Transition-state Structures. Part III. Sulfonyl Transfer Reactions
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A kinetic spectrophotometric study has been performed on the reactions of p-nitrophenyl benzenesulfonate (PNPBS) with m-chlorophenoxide, p-chlorophenoxide, phenoxide, p-methylphenoxide and p-methoxyphenoxide ions in DMSO-H2O mixtures at 25.0 deg C.Systema
- Tarkka, Richard M.,Park, William K. C.,Liu, Ping,Buncel, Erwin,Hoz, Shmaryahu
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p. 2439 - 2444
(2007/10/02)
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- 1-Phenylsulfonylbenzotriazole: A novel and convenient reagent for the preparation of benzenesulfonamides and aryl benzenesulfonates
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Readily available 1-phenylsulfonylbenzotriazole smoothly converts various aliphatic and aromatic amines and phenols into the corresponding benzenesulfonamides and benzenesulfonates in good yields.
- Katritzky,Zhang,Wu
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p. 205 - 216
(2007/10/02)
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- Metal ion catalysis in nucleophilic displacement reactions at carbon, phosphorus, and sulfur centers.1 4. Mechanism of the reaction of aryl benzenesulfonates with alkali-metal ethoxides: Catalysis and inhibition by alkali-metal ions
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The rates of the nucleophilic displacement reactions of aryl benzenesulfonates (1a-f) with alkali-metal ethoxides (LiOEt, KOEt, and KOEt in the presence of completing agents) in anhydrous ethanol at 25 °C have been studied by spectrophotometric techniques. For all esters studied, the order of reactivity is LiOEt - +) and inhibition (Li+) are proposed to occur via reactive alkali-metal ethoxide ion pairs. Second-order rate constants for free ethoxide and metal-ethoxide ion pairs are calculated. Hammett treatment of leaving-group effects results in correlation of rate data with σ0 substituent constants and large ρ values of 3.0 (KOEt), 3.1 (LiOEt), and 3.4 (EtO-). A rate-determining transition state having well-advanced EtO-S bond formation but little S-OAr bond breakage is proposed. The similarity of the ρ values for KOEt, LiOEt, and EtO- implies that alkali-metal ions do not significantly alter the extent of S-OAr bond breakage in the transition state. However, metal ions do stabilize the transition state to differing degrees. Equilibrium constants for association of K+ and Li+ with the transition state are calculated, and it is concluded from the relative magnitudes of these values (Li+ +) that solvated metal ions interact with the transition state, rather than bare metal ions. Hammett plots of the free energy of association of metal ions with the transition state indicate that leaving-group substituent effects on metal ion binding in the transition state are small (ρ = -0.39 (K+) and -0.23 (Li+)) and lead to the conclusion that more electron-rich transition states bind metal ions more strongly.
- Pregel, Marko J.,Dunn, Edward J.,Buncel, Erwin
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p. 3545 - 3550
(2007/10/02)
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- CATALYTIC EFFECT OF PYRIDINE BASES IN REACTIONS LEADING TO THE FORMATION OF PHENYL ESTERS OF AROMATIC SULFONIC ACIDS
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The sulfonylation of p-chlorophenol by p-bromobenzenesulfonyl chloride in the presence of pyridine bases in nitrobenzene was investigated by potentiometric titration.A linear relation was obtained butween the logarithms of the catalytic constants and the basicity of the catalysts (β = 1.04) and the sensitivity of the reaction to the effect of substituents in the pyridine (ρ = -6.5).The effect of the leaving group (the kBrc/kClc ratio) is large and equal to 33.5.On the basis of the obtained data and of previous investigations it is suggested that catalysis by pyridine bases in the sulfonylation of phenols has a nucleophilic mechanism.
- Vizgert, R.V.,Maksimenko, N.N.,Panov, E.P.
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p. 520 - 524
(2007/10/02)
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- KINETICS OF SULFONYLATION OF SUBSTITUTED PHENOLS IN THE PRESENCE OF TRIETHYLAMINE
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The rate constants for the sulfonation of meta- and para-substituted phenols by benzenesulfonyl chloride in the presence of triethylamine in benzene were determined.The dependence of the rate constants on the Hammett ? constants has a V-shaped form.The effect of the leaving group was investigated, and the kinetic isotope effect was determined.The possibility of reaction by two catalytic paths (nucleophilic and general base catalysis) is discussed, and proposals were made about the reaction mechanism.
- Vizgert, R. V.,Maksimenko, N. N.,Krut'ko, I. N.
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p. 1247 - 1252
(2007/10/02)
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