- Poly(S-ethylsulfonyl- l -homocysteine): An α-Helical Polypeptide for Chemoselective Disulfide Formation
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Homocysteine and cysteine are the only natural occurring amino acids that are capable of disulfide bond formations in peptides and proteins. The chemoselective formation of asymmetric disulfide bonds, however, is chemically challenging and requires an activating group combining stability against hard nucleophiles, e.g., amines, with reactivity toward thiols and soft nucleophiles. In light of these considerations, we introduced the S-alkylsulfonyl cysteines in our previous work. Here, we present the synthesis and ring-opening polymerization of S-ethylsulfonyl-l-homocysteine N-carboxyanhydrides. We demonstrate that the polymerization leads to narrowly distributed polypeptides (D= 1.1-1.3) with no detectable side reactions in a chain length regime from 11 to 165. In contrast to the already reported cysteine derivatives, poly(S-ethylsulfonyl-l-homocysteine)s do not form β-sheets, which reduce solubility and limit the degree of polymerization of poly(S-ethylsulfonyl-l-cysteine)s to 50. Instead, these polymers form α-helices as confirmed by circular dicroism (CD) experiments and infrared spectroscopy (FT-IR). In comparison to the cysteine derivatives, the α-helix formation leads to slightly faster polymerization kinetics (rate constants from 1.44 × 10-5 to 5.29 × 10-5 s-1). In addition, the ability for the chemoselective formation of asymmetric disulfides is preserved as monitored via 1H NMR experiments. Consequently, this new polypeptide overcomes the chain length limitations of poly(S-ethylsulfonyl-l-cysteine)s and thus provides convenient access to reactive poly(S-ethylsulfonyl-l-homocysteine)s for chemoselective disulfide formation.
- Muhl, Christian,Sch?fer, Olga,Bauer, Tobias,R?der, Hans-Joachim,Barz, Matthias
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- Copper-Catalyzed N-Directed Distal C(sp3)-H Sulfonylation and Thiolation with Sulfinate Salts
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We herein report a selective and catalytic C(sp3)-H functionalization approach to access amines bearing organo-sulfonyl and organo-thiol groups. This reaction proceeds through a cascade process of N-radical formation, alkyl radical formation via 1,5-HAT, and C-S bond formation, thereby offering a series of functionalized amines. This method could enable primary, secondary, and tertiary C(sp3)-H sulfonylation and thiolation and also exhibits good functional group tolerance.
- Chen, Guang-Le,He, Shi-Hui,Cheng, Liang,Liu, Feng
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supporting information
p. 8338 - 8342
(2021/10/25)
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- Visible-Light-Driven Sulfonation of α-Trifluoromethylstyrenes: Access to Densely Functionalized CF3-Substituted Tertiary Alcohol
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Reported herein is a visible-light-induced sulfonation of α-trifluoromethylstyrenes with sodium sulfinates, which provides a series of α-trifluoromethyl-β-sulfonyl tertiary alcohols. This new synthetic protocol is enabled by a charge-transfer complex between oxygen and sulfinates, featuring broad substrate scope and scalability. Excellent functional group compatibility and chemoselectivity render this method suitable for sulfonation of pharmaceutically relevant molecules. In the presence of D2O, deuteriotrifluorinated products were also obtained, further demonstrating the flexibility and synthetic potentials of this strategy.
- Chen, Yi-Xuan,Wang, Zhu-Jun,Xiao, Jun-An,Chen, Kai,Xiang, Hao-Yue,Yang, Hua
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supporting information
p. 6558 - 6562
(2021/08/23)
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- Preparation method of substituted sulfinate
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The invention discloses a preparation method of substituted sulfinate, which comprises the following steps: by using substituted sulfonyl chloride as a raw material, carrying out hydrolysis reductionreaction on the substituted sulfonyl chloride in water in the presence of a reducing agent and an acid-binding agent to generate the corresponding substituted sulfinate. The method is a novel method which is easy to implement and suitable for industrial scale production and is used for preparing sulfinate and derivatives thereof. The method is simple in technological process, high in product purity and safe and environment-friendly, wherein the waste gas, solid and liquid are easy to treat.
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Paragraph 0023-0029
(2020/12/30)
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- Direct sulfonylation of BODIPY dyes with sodium sulfinates through oxidative radical hydrogen substitution at the α-position
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An efficient and convenient protocol for the direct sulfonylation of BODIPY dyes with sodium sulfinates via a radical process is described for the first time. This transformation presented wide substrate scope and high regioselectivity, providing a series of α-sulfonylated BODIPYs. Meaningfully, the sulfonyl group, as a good leaving group, allowed the facile introduction of a variety of functionalities on the BODIPY core. Moreover, a 2,4-dinitrobenzenesulfonyl (DBS) group substituted BODIPY showed dramatically quenched fluorescence via the photoinduced electron transfer (PET) pathway, and was demonstrated as a new fluorescent probe for selective biothiol detection. This journal is
- Lv, Fan,Guo, Xing,Wu, Hao,Li, Heng,Tang, Bing,Yu, Changjiang,Hao, Erhong,Jiao, Lijuan
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supporting information
p. 15577 - 15580
(2020/12/30)
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- A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides
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A convenient and e?cient synthesis of sulfones from sulfinates and aryl halides was developed. The reaction occurred under UV irradiation without transition metal catalyst or photocatalyst. A radical pathway via single-electron transfer (SET) of electron donor-acceptor (EDA) complex was proposed based on UV-vis spectroscopy, radical inhibiting and trapping experiments. (Figure presented.).
- Chen, Lei,Liang, Jie,Chen, Zhen-yu,Chen, Jie,Yan, Ming,Zhang, Xue-jing
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supporting information
p. 956 - 960
(2019/01/25)
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- Regio- and Enantioselective Preparation of Chiral Allylic Sulfones Featuring Elusive Quaternary Stereocenters
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We describe here the first general asymmetric synthesis of sterically encumbered α,α-disubstituted allylic sulfones via Pd-catalyzed allylic substitution. The design and application of a new and highly efficient phosphoramidite ligand (L10) proved to be crucial, and a wide variety of challenging allylic sulfones featuring quaternary stereocenters could be obtained in good yields and with good to excellent levels of regio- and enantioselectivities under attractive process conditions. The developed methodology employs easily accessible chemical feedstock including racemic allylic precursors and sodium sulfinates. The utility of the method is further demonstrated by the synthesis of the sesquiterpene (?)-Agelasidine A.
- Cai, Aijie,Kleij, Arjan W.
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supporting information
p. 14944 - 14949
(2019/11/05)
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- Direct Substitution of Secondary and Tertiary Alcohols to Generate Sulfones under Catalyst- and Additive-Free Conditions
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An environmentally benign protocol that affords propargylic sulfones containing highly congested carbon centers from easily accessible alcohols and sulfinic acids with water as the only byproduct is reported. The reaction proceeded via an in situ dehydrative cross-coupling process by taking advantage of the synergetic actions of multiple hydrogen bonds rather than relying on an external catalyst and/or additives to achieve high product distribution.
- Liu, Yanan,Xie, Peizhong,Sun, Zuolian,Wo, Xiangyang,Gao, Cuiqing,Fu, Weishan,Loh, Teck-Peng
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supporting information
p. 5353 - 5356
(2018/09/13)
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- METHOD FOR PRODUCING PYRIDINE COMPOUND
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A pyridine compound represented by formula (1) that is useful as an insecticide is produced by reacting a compound represented by formula (2) and a compound represented by formula (3). In formula (2) L1 represents a halogen atom; R2, R3, R4, R5, and R6 represent chain hydrocarbon groups, etc., having 1-6 carbon atoms optionally substituted by fluorine atoms; A1 represents —NR7—, an oxygen atom, or a sulfur atom; A2 represents a nitrogen atom or ═CR8—; and R7 and R8 represent C1-6 chain hydrocarbon groups or hydrogen atoms. In formula (3) M+ represents a sodium ion, a potassium ion, or a lithium ion.
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Paragraph 0105
(2017/06/28)
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- Rethinking Cysteine Protective Groups: S-Alkylsulfonyl-l-Cysteines for Chemoselective Disulfide Formation
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The ability to reversibly cross-link proteins and peptides grants the amino acid cysteine its unique role in nature as well as in peptide chemistry. We report a novel class of S-alkylsulfonyl-l-cysteines and N-carboxy anhydrides (NCA) thereof for peptide synthesis. The S-alkylsulfonyl group is stable against amines and thus enables its use under Fmoc chemistry conditions and the controlled polymerization of the corresponding NCAs yielding well-defined homo- as well as block co-polymers. Yet, thiols react immediately with the S-alkylsulfonyl group forming asymmetric disulfides. Therefore, we introduce the first reactive cysteine derivative for efficient and chemoselective disulfide formation in synthetic polypeptides, thus bypassing additional protective group cleavage steps.
- Sch?fer, Olga,Huesmann, David,Muhl, Christian,Barz, Matthias
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supporting information
p. 18085 - 18091
(2016/12/16)
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- Eosin Y (EY) Photoredox-Catalyzed Sulfonylation of Alkenes: Scope and Mechanism
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Alkyl- and aryl vinyl sulfones were obtained by eosin Y (EY)-mediated visible-light photooxidation of sulfinate salts and the reaction of the resulting S-centered radicals with alkenes. Optimized reaction conditions, the sulfinate and alkene scope, and X-ray structural analyses of several reaction products are provided. A detailed spectroscopic study explains the reaction mechanism, which proceeds through the EY radical cation as key intermediate oxidizing the sulfinate salts.
- Meyer, Andreas Uwe,Straková, Karolína,Slanina, Tomá?,K?nig, Burkhard
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supporting information
p. 8694 - 8699
(2016/07/07)
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- Cu-Catalyzed Deoxygenative C2-Sulfonylation Reaction of Quinoline N-Oxides with Sodium Sulfinate
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An unexpected Cu-catalyzed deoxygenative C2-sulfonylation reaction of quinoline N-oxides in the presence of radical initiator K2S2O8 was developed that used sodium sulfinate as a sulfonyl coupling partner. The mechanism studies indicate that the reaction proceeds via Minisci-like radical coupling step to give sulfonylated quinoline with good chemical yields.
- Du, Bingnan,Qian, Ping,Wang, Yang,Mei, Haibo,Han, Jianlin,Pan, Yi
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supporting information
p. 4144 - 4147
(2016/08/30)
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- First palladium-catalyzed denitrated coupling of nitroarenes with sulfinates
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The first example of palladium-catalyzed protocol for the denitrated coupling of nitroarenes with sulfinates was developed, achieving aryl and heterocyclic sulfones in moderate to excellent yields. The cyclopalladated ferrocenylimine (I) exhibited highly catalytic activity for this transformation with low catalyst loading (0.75 mol %). The efficiency of this reaction was demonstrated by compatibility with a wide range of groups. Thus, the method represents a simple and facile procedure to access aryl and heterocyclic sulfones.
- Tian, Heng,Cao, Aijuan,Qiao, Lijun,Yu, Ajuan,Chang, Junbiao,Wu, Yangjie
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supporting information
p. 9107 - 9112
(2015/03/05)
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- One-pot synthesis of symmetric 1,7-dicarbonyl compounds via a tandem radical addition-elimination-addition reaction
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A novel approach to synthesize symmetric 1,7-dicarbonyl compounds via a tandem radical addition-elimination-addition reaction of S-carbonylmethyl xanthates with allylmethylsulfone and its analogues has been developed. Radicals were produced from S-carbonylmethyl xanthates by adding dilauroyl peroxide and reacted with allylmethylsulfone or analogues to generate terminal olefins as intermediates. The excessive radicals reacted with the intermediate olefins immediately to give adducts of symmetric 1,7-dicarbonyl compounds. This is an efficient method to synthesize 1,7-dicarbonyl compounds under mild conditions. The Royal Society of Chemistry 2013.
- Huang, Zhongyan,Xu, Jiaxi
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p. 15114 - 15120
(2013/09/02)
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- PYRIDYL INHIBITORS OF HEDGEHOG SIGNALLING
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The invention provides novel inhibitors of hedgehog signaling that are useful as s therapeutic agent for treating malignancies where the compounds have the general formula (I): where A, X, Y R1, R2, R3, R4, m and n are as described herein.
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Page/Page column 132
(2009/11/29)
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- Pyridyl inhibitors of hedgehog signalling
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The invention provides novel inhibitors of hedgehog signaling that are useful as a therapeutic agents for treating malignancies where the compounds have the general formula I: wherein A, X, Y R1, R2, R3, R4, m and n are as described herein.
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Page/Page column 95
(2010/10/20)
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- Sulfur containing compounds
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This invention is directed to novel and known stufur containing compounds and pharmaceutically acceptable salts thereof that have utility as antifungals and as antiproliferative agents against mammalian cells, in particular cancer cells and most particularly leukemia-derived cells. The invention provides a method for synthesizing certain of the sulfur containing compounds that is more efficient than previously known methods.
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Page/Page column 30
(2010/11/30)
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- Antifungal thiosulfonates: Potency with some selectivity
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A series of thiosulfonates have been prepared and tested against Aspergillus niger and Aspergillus flavus. In general, the thiosulfonates are moderate antifungal agents - more potent than corresponding inactive disulfides and less potent than corresponding very active fungitoxic disulfides. A pair of thiosulfonates show high selectivity, each killing only one kind of fungus. CSIRO 2000.
- Baerlocher, Felix Jakob,Baerlocher, Mark Otto,Chaulk, Crystal Lee,Langler, Richard Francis,MacQuarrie, Stephanie Lee
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p. 399 - 402
(2007/10/03)
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- 3-Sulfonyl-1-carba-1-dethiacephems
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The stability of the 1-carba-1-dethiacephalosporin framework has allowed the synthesis of a range of 3-sulfonyl-1-carba-1-dethiacephems unavailable for a variety of reasons in the cephem arena.The known p-nitrobenzyl 7β-(phenylacetamido)-3-oxy>-1-carba-1-dethia-3-cephem-4-carboxylate served as a precursor to this series of compounds.Displacement of the enol triflate with various sulfinates in acetonitrile or DMF and deprotection of the intermediates led to 7β-amino>-3--1-carba-1-dethia-3-cephem-4-carboxylic acids.The 3-sulfonyl-1-carba-1-dethiacephems display potent activity against both Gram-positive and Gram-negative bacteria.The following MIC's (μg/mL) for the 3-cyclopropyl sulfone are representative: Staphylococcus aureus = 4, Streptococcus pyogenes = 1, Haemophilus influenzae = 0.25, Escherichia coli = 0.03, Enterobacter cloacae = 0.25, Proteus rettgeri = 0.25.The excellent in vitro antibacterial activity of this series indicates the potential of the carbacephalosporin framework for exploring substituents which are unknown or which produce unstable cephems.
- Crowell, Thomas A.,Halliday, Basil D.,McDonald, John H.,Indelicato, Joseph M.,Pasini, Carol E.,Wu, Ernie C. Y.
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p. 2436 - 2442
(2007/10/02)
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- Organic sulfur mechanisms. 24. Preparation and reaction of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride
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2-Hydroxyethanesulfonyl chloride (1a) is readily made by reaction of an aqeous solution of 2-mercaptoethanol (4a) with chlorine.This is the first clearly proved preparation of a compound which is both an alcohol and a sulfonyl chloride.Reactions of 1a with water and alcohols evidently proceed largely by intramolecular cyclization to the transient β-sultone (2a), which then undergoes nucleophilic ring opening to form the products.In the presence of tertiary amines a minor but significant part of the reaction is shown by deuterium labelling to proceed via hydroxymethylsulfene (14), the principal reaction of which is simply to add the alcohol or water; only a small part, if any, of the sulfene (14) loses the hydroxyl group to give the ethenesulfonate derivatives (13 or 22).Aqueous chlorination of 3-mercapto-1-propanol gave 3-chloro-1-propanesulfonyl chloride (5a) and 1,3-propane sultone (2b) with no sign of any 3-hydroxy-1-propanesulfonyl chloride (1b).A mechanism for the aqueous chlorination process invoking a cyclic chlorooxasulfoxonium ion (27) is discussed.
- King, James Frederick,Hillhouse, John Henry
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p. 1583 - 1593
(2007/10/02)
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