17414-08-3Relevant articles and documents
A novel phenylsulfenylation of unsaturated acids or alcohols by methyl phenyl sulfoxide and substoichiometric (COCl)2
Liang, Sen,Liu, Yongguo,Sun, Baoguo,Tian, Hongyu,Wang, Hao,Wang, Yinong,Wang, Yutong,Xiang, Fan
supporting information, (2022/01/03)
Phenylsulfenylation of unsaturated acids and alcohols has been achieved by methyl phenyl sulfoxide (PhSOCH3) and substoichiometric (COCl)2 in CH3CN. The corresponding cyclization products, lactones with a phenylthio group from unsaturated acids were obtained in mediate to good yields, whereas the cyclic ethers with a phenylthio group from unsaturated alcohols in relatively low yields. PhSOH was proposed to be the key active species for phenylsulfenylation, which was generated in situ by the reaction of PhSOCH3 with substiochiometric amount of (COCl)2. Anhydrous HCl could replace (COCl)2 in the reactions to give the comparable results.
Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations
Dong, Xichang,Roeckl, Johannes L.,Waldvogel, Siegfried R.,Morandi, Bill
, (2021/02/12)
Vicinal dibromides and dichlorides are important commodity chemicals and indispensable synthetic intermediates in modern chemistry that are traditionally synthesized using hazardous elemental chlorine and bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions that can be used both to synthesize useful dihalogenated molecules from simple alkenes and to recycle waste material through retro-dihalogenation. The reaction is demonstrated using 1,2-dibromoethane, as well as 1,1,1,2-tetrachloroethane or 1,2-dichloroethane, to dibrominate or dichlorinate, respectively, a wide range of alkenes in a simple setup with inexpensive graphite electrodes. Conversely, the hexachlorinated persistent pollutant lindane could be fully dechlorinated to benzene in soil samples using simple alkene acceptors.
Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
Saavedra, Beatriz,Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
supporting information, p. 3462 - 3467 (2020/06/04)
This study describes a novel and catalyst-free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non-toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing their reactivity, as well as, the recyclability of the reaction medium for at least 5 consecutive cycles. Thus, this versatile strategy uses non-toxic reagents without the need of metal catalysts in a sustainable solvent, being an interesting alternative to traditional hazardous protocols.
Fenton-Inspired C-H Functionalization: Peroxide-Directed C-H Thioetherification
Groendyke, Brian J.,Modak, Atanu,Cook, Silas P.
, p. 13073 - 13091 (2019/10/10)
Substoichiometric iron mediates the thioetherification of unactivated aliphatic C-H bonds directed by resident silylperoxides. Upon exposure to a catalytic amount of iron(II) triflate, TIPS-protected peroxides bearing primary, secondary, and tertiary C-H sites undergo chemoselective thioetherification of remote C-H bonds with diaryl disulfides. The reaction demonstrates a broad substrate scope and functional group tolerance without the use of any noble metal additives. Mechanistic experiments suggest that the reaction proceeds through 1,5-H atom abstraction by a hydroxyl radical generated with iron.
Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (?)-Cyclosmenospongine
Speck, Klaus,Magauer, Thomas
supporting information, p. 1157 - 1165 (2017/02/05)
We report a full account on the development of a unique cationic polyene cyclization for the total synthesis of the tetracyclic meroterpenoid (?)-cyclosmenospongine. A highly convergent three-component coupling strategy enabled rapid access to individual cyclization precursors that were tested for their reactivity. The successful transformation generates three rings and sets four consecutive stereocenters in a single operation proceeding in a highly efficient manner to give exclusively the trans-decalin framework. In addition, we found that the enol ether geometry and the relative configuration of C3 and C8 are crucial for the success of the polyene cyclization.
Deep Eutectic Solvents as Reaction Media for the Palladium-Catalysed C?S Bond Formation: Scope and Mechanistic Studies
Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
supporting information, p. 10522 - 10526 (2017/08/10)
A unique jigsaw catalytic system based on deep eutectic solvents and palladium nanoparticles where C?S bonds are formed from aryl boronic acids and sodium metabisulfite, is introduced. The functionalization step is compatible with a broad spectrum of reagents such as nucleophiles, electrophiles or radical scavengers. This versatile approach allows the formation of different types of products in an environmentally friendly medium by selecting the components of the reaction, which engage one with another as pieces in a jigsaw. This simple procedure avoids the use of toxic volatile organic solvents allowing the formation of complex molecules in a one-pot reaction under mild conditions. Despite the fact that only 1 mol % of metal loading is used, the recyclability of the catalytic system is possible. Kinetic experiments were performed and the reaction order for all reagents, catalyst and ligand was determined. The obtained results were compared to palladium nanocrystals of different known shapes in order to shed some light on the properties of the catalyst.
Copper-Catalyzed Oxysulfenylation of Enolates with Sodium Sulfinates: A Strategy to Construct Sulfenylated Cyclic Ethers
Gao, Yinglan,Gao, Yang,Tang, Xiaodong,Peng, Jianwen,Hu, Miao,Wu, Wanqing,Jiang, Huanfeng
supporting information, p. 1158 - 1161 (2016/03/15)
A new copper-catalyzed oxysulfenylation reaction of enolates with sodium sulfinates has been disclosed. A series of sulfenylated heterocycles including four- and seven-membered cyclic ether were obtained in mild to good yields. This reaction is proposed to go through a radical process, and the sulfur radical (RS?) may be a reactive species.
Cyclofunctionalization of unsaturated alcohols, phenols, acids, and sulfonamides with 1-benzene-sulfinyl piperidine and trifluoromethanesulfonic anhydride
Crich, David,Surve, Bhushan,Sannigrahi, Mousumi
, p. 827 - 830 (2007/10/03)
The combination of a benzenesulfinamide, trifluoromethanesulfonic anhydride, and Huenig's base brings about the cyclofunctionalization of unsaturated alcohols, phenols, acids, and sulfonamides to give the corresponding α-phenylsulfanylmethyl cyclic ethers, lactones and sulfonamides, respectively. In an unanticipated twist the products are isolated at the sulfur (II) oxidation state denoting an overall reduction in the oxidation state of the sulfur based electrophile in the course of the reaction.
Reaction of 4′-nitrobenzenesulfenanilide (NBSA) with Lewis acids. A study of its application in sulfenocyclization of alkenes and alkynes
Benati, Luisa,Capella, Laura,Montevecchi, Pier Carlo,Spagnolo, Piero
, p. 12395 - 12406 (2007/10/02)
Phenylsulfenocyclization of a number of alkenes and alkynes possessing internal hydroxyl, carboxyl or vinyl functionality has been investigated with NBSA. Thioetherification of 4-penten-1-ol 4 as well as thiolactonization of 4-penten-1-oic acid 7 and, to a modest extent, 4-pentyn-1-oic acid 8 can be successfully achieved with NBSA in the presence of boron trifluoride. On the other hand, under analogous conditions 3-buten-1-ol 3 and 3-buten-1-oic acid 6 fail to undergo thiocyclization and give instead oxa- and/or aza-sulfenylation 1,2-adducts. Similar failure is observed with 4-pentyn-1-ol 5, in which case diphenyl disulfide and 4-nitroaniline are the exclusive products. Hexa-1,5-diene 9, to some extent, affords a cyclized arylaminosulfide, i.e. 23, ascribable to formal loss of a methylene unit from the initial (phenylthiomethyl)- cyclopentyl cation 24. The reaction products are discussed in terms of intermediate thiiranium and thiirenium ions whose decomposition mode is strictly dependent upon their structural features. Novel evidence is also presented that aluminium chloride and bromide can promote reaction of NBSA with alkenes and alkynes to afford chloro- and bromo-sulfenylation adducts in varying yields.
