4358-63-8Relevant academic research and scientific papers
Practical Electro-Oxidative Sulfonylation of Phenols with Sodium Arenesulfinates Generating Arylsulfonate Esters
Tian, Zhibin,Gong, Qihang,Huang, Tianzeng,Liu, Long,Chen, Tieqiao
, p. 15914 - 15926 (2021/05/04)
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.
Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups
Perez, Kaitlyn A.,Rogers, Cameron R.,Weiss, Emily A.
supporting information, p. 14091 - 14095 (2020/06/08)
This Communication describes the use of CuInS2/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.
Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride
Laudadio, Gabriele,Bartolomeu, Aloisio De A.,Verwijlen, Lucas M. H. M.,Cao, Yiran,De Oliveira, Kleber T.,No?l, Timothy
, p. 11832 - 11836 (2019/08/26)
Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, the development of novel and efficient synthetic methods to access these functional groups is of great interest. Herein, we report a mild and environmentally benign electrochemical approach to prepare sulfonyl fluorides using thiols or disulfides, as widely available starting materials, in combination with KF, as an inexpensive, abundant and safe fluoride source. No additional oxidants nor additional catalysts are required and, due to mild reaction conditions, the reaction displays a broad substrate scope, including a variety of alkyl, benzyl, aryl and heteroaryl thiols or disulfides.
Deprotection of durable benzenesulfonyl protection for phenols — efficient synthesis of polyphenols
Alam, Mohammad Shariful,Koo, Sangho
supporting information, p. 247 - 254 (2018/01/08)
A robust protection method for phenol was demonstrated by the use of durable benzenesulfonyl group, which survives various harsh reaction conditions using Grignard reagent, organolithium reagent, metal alkoxide, phosgene, mineral, and Lewis acids. A facile deprotection condition utilizing pulverized KOH (5 equiv) and t-BuOH (10 equiv) in hot toluene makes this protocol as a practical method, which can be applied to the multistep synthesis of biologically and medicinally important polyphenol compounds.
Synthetic method of benzenesulfonate derivative
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Paragraph 0020; 0021; 0023, (2018/05/03)
The invention relates to a synthetic method of a benzenesulfonate derivative and belongs to the technical field of synthesis of compounds. A compound (described in the specification) is taken as raw materials, and reaction is carried out with ethylene glycol or R2-OH to generate a compound (described in the specification), wherein R1 is selected from alkyl, H or F, and R2 is selected from allyl, propargyl or benzene. The synthetic method provided by the invention comprises the following concrete operations: adding ethylene glycol or R2-OH and dichloromethane into a reactor, adding organic alkali while stirring, then cooling to the temperature below 15 DEG C, starting to dropwise add a substance (described in the specification), after the substance is dropwise added, returning to room temperature and further stirring for 0.5-1 hour, then heating and carrying out reflux reaction for 1-2 hours, after the reflux reaction is complete, carrying out ice thawing treatment, layering, drying, and concentrating, so that the benzenesulfonate derivative product is obtained. The synthetic method provided by the invention is simple, reaction process is mild and stable, yield is high, and the obtained product is high in purity.
Benzenesulfonylation reagent as well as preparation method and application thereof
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Paragraph 0042; 0043; 0044; 0054; 0055; 0056, (2017/07/21)
The invention discloses a benzenesulfonylation reagent. The structure of the benzenesulfonylation reagent is shown as formula I in the specification, wherein R is a benzene ring connected with 0-5 substituents, and the substituents on the benzene ring are chlorine atoms, fluorine atoms, methyl groups or tert-butyl groups independently. The invention further discloses a preparation method and an application of the benzenesulfonylation reagent. The benzenesulfonylation reagent is prepared from methoxyamine hydrochloride and benzenesulfonyl chloride or a benzenesulfonyl chloride derivative through two steps of reactions, raw materials are cheap, a preparation process is simple, reaction conditions are mild, few side effects are produced, only extraction and simple column chromatographic purification are needed for aftertreatment, and the yield is high. The benzenesulfonylation reagent has higher benzenesulfonylation activity, benzenesulfonylation reaction conditions are mild, a reaction substrate range is wider, compounds such as alcohol, phenol, naphthol, thiophenol and the like can be subjected to a benzenesulfonylation reaction in presence of acetonitrile neutralized potassium carbonate, and -C1 does not exist on the benzenesulfonylation reagent, so that HCl gas with pungent odor cannot be emitted during application.
Dimerization of Aryl Sulfonates by in situ Generated Nickel(0)
Maddaluno, Jacques,Durandetti, Muriel
supporting information, p. 2385 - 2388 (2015/10/19)
A mild and user-friendly nickel-catalyzed method for the reductive homocoupling of aromatic tosylates is presented. The reaction proceeds between room temperature and 60 °C, with stable substrates (ArOTs) easily prepared from inexpensive and commercially available phenols or naphthols. It relies on a catalytic amount (10 mol%) of a robust catalyst (NiBr2bipy) that does not require the preparation of sensitive organometallic intermediates. Yields are good to excellent.
Kinetic and computational evidence for an intermediate in the hydrolysis of sulfonate esters
Babtie, Ann C.,Lima, Marcelo F.,Hollfelder, Florian,Kirby, Anthony J.
, p. 8095 - 8101,7 (2012/12/11)
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.
Highly efficient Pd-catalyzed cyanation of aryl chlorides and arenesulfonates with potassium ferrocyanide in aqueous media
Zhang, Junli,Chen, Xiaorong,Hu, Tongjie,Zhang, Yuan,Xu, Kunling,Yu, Yanpeng,Huang, Jun
experimental part, p. 56 - 60 (2011/01/12)
A highly improved Pd-catalyzed cyanation of aryl chlorides to corresponding benzonitriles was demonstrated in aqueous media. Moreover, Pd-catalyzed cyanation of aryl tosylates and benzenesulfonates with K4[Fe(CN) 6] was developed under the similar conditions, which extended application scope of the cyanation. Graphical Abstract: [Figure not available: see fulltext.]
A new preparative method of aryl sulfonate esters by using cyclic organobismuth reagents
Sakurai, Naoto,Mukaiyama, Teruaki
, p. 771 - 790 (2008/09/18)
A new method for the preparation of aryl sulfonate esters by using a cyclic pentavalent bismuth is described. Aryl sulfonate esters are formed in good to high yields by treating 10-arylphenothiabismine 5,5-dioxides, m-chloroperoxybenzoicacid (m-CPBA)and various sulfonic acids in dichloromethane.
