- High Chemoselectivity in the Construction of Aryl Methyl Sulfones via an Unexpected C-S Bond Formation between Sulfonylhydrazides and Dimethyl Phosphite
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A highly chemoselective route to aryl methyl sulfones via an unexpected C S bond formation between sulfonylhydrazides and dimethyl phosphite catalyzed by NaI under mild conditions has been established. This transformation provides an alternative and metal-free pathway to acquire various aryl methyl sulfones in good to excellent yields. Notably, dimethyl phosphite was employed as a stable and readily available alkyl source.
- Liu, Teng,Yu, Shiwen,Shen, Xiang,Li, Yixian,Liu, Jianjun,Huang, Chao,Cheng, Feixiang
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p. 153 - 160
(2021/10/04)
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- Primary Sulfonamide Functionalization via Sulfonyl Pyrroles: Seeing the N?Ts Bond in a Different Light
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Despite common occurrence in molecules of value, methods for transforming sulfonamides are distinctly lacking. Here we introduce easy-to-access sulfonyl pyrroles as synthetic linchpins for sulfonamide functionalization. The versatility of the sulfonyl pyrrole unit is shown by generating a variety of products through chemical, electrochemical and photochemical pathways. Preliminary results on the direct functionalization of primary sulfonamides are also provided, which may lead to new modes of activation.
- Ozaki, Tomoya,Yorimitsu, Hideki,Perry, Gregory J. P.
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supporting information
p. 15387 - 15391
(2021/10/04)
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- Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation
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A safe, practical and eco-friendly method for the switchable synthesis of sulfoxides and sulfones through visible-light-initiated oxygenation of sulfides at ambient temperature under transition-metal-, additives-free and minimal solvent conditions. The synergistic catalytic efforts between CF3SO2Na and 2-butoxyethyl ether represents the key promoting factor for the reaction. This journal is
- Liu, Kai-Jian,Wang, Zheng,Lu, Ling-Hui,Chen, Jin-Yang,Zeng, Fei,Lin, Ying-Wu,Cao, Zhong,Yu, Xianyong,He, Wei-Min
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supporting information
p. 496 - 500
(2021/01/28)
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- General sulfone construction: Via sulfur dioxide surrogate control
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A highly efficient one-step synthesis of alkyl-alkyl and aryl-alkyl sulfones with a facile combination of halides, sulfur dioxide surrogates and phosphate esters is described. When thiourea dioxide was employed as a reductive sulfur dioxide surrogate, alkyl-alkyl sulfones were obtained under transition metal free conditions. Aryl-alkyl sulfones were obtained with an extremely low catalytic loading (0.2 mol%) via altering the mask of sulfur dioxide surrogates to sodium dithionite. A phosphate ester was employed as a stable and readily available alkyl source. Notably, this protocol has been applied to the late-stage modification of natural products and bioactive molecules.
- Chen, Shihao,Li, Yaping,Wang, Ming,Jiang, Xuefeng
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supporting information
p. 322 - 326
(2020/02/13)
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- HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
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Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
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Paragraph 0293-0294
(2019/05/15)
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- A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid Salts under Mild Conditions
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The amide derived from 4-hydroxy-l-proline and 2,6-dimethylaniline is a powerful ligand for Cu-catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing the formation of a wide range of (hetero)aryl sulfones from the corresponding (hetero)aryl halides at considerably low catalytic loadings. The coupling of (hetero)aryl iodides and sodium methanesulfinate proceeds at room temperature with only 0.5 mol % CuI and ligand, representing the first example for Cu-catalyzed arylation at both low catalytic loading and room temperature.
- Zhao, Jinlong,Niu, Songtao,Jiang, Xi,Jiang, Yongwen,Zhang, Xiaojing,Sun, Tiemin,Ma, Dawei
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p. 6589 - 6599
(2018/05/31)
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- A novel synthesis of aryl methyl sulfones and β-hydroxysulfones from sodium sulfinates and di-tert-butyl peroxide in H2O medium
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A novel and convenient synthetic route for aryl methyl sulfones and β-hydroxysulfones was developed via the radical reaction between sodium sulfinates and di-tert-butyl peroxide (DTBP). Without any catalysts and additives, the synthetic process could be smoothly carried out to afford the target products in good to excellent yields in H2O medium, demonstrating its promising application. In the present system, H2O could act not only as a green solvent but also as a reactant.
- Lai, Junyi,Yuan, Gaoqing
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supporting information
p. 524 - 527
(2018/01/10)
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- Manganese-catalyzed directed methylation of C(sp2)-H bonds at 25 °C with high catalytic turnover
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We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl2· 2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 103, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.
- Sato, Takenari,Yoshida, Takumi,Al Mamari, Hamad H.,Ilies, Laurean,Nakamura, Eiichi
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supporting information
p. 5458 - 5461
(2017/11/06)
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- Copper-catalyzed: S -methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water
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A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP was efficiently developed, providing a variety of methyl sulfones with good to excellent yields. The reaction can be carried out in water smoothly without any ligand or additive under mild conditions and this catalyst-in-water can be recycled several times.
- Yang, Yu,Bao, Yajie,Guan, Qianqian,Sun, Qi,Zha, Zhenggen,Wang, Zhiyong
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p. 112 - 116
(2017/08/15)
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- Copper-catalyzed aerobic oxidation and cleavage/formation of C-S bond: A novel synthesis of aryl methyl sulfones from aryl halides and DMSO
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With atmospheric oxygen as the oxidant, a novel copper(i)-catalyzed synthesis of aryl methyl sulfones from aryl halides and widely available DMSO is described. The procedure tolerates aryl halides with various functional groups (such as methoxy, acetyl, chloro, fluoro and nitro groups), which could afford aryl methyl sulfones in moderate to high yields. The copper-catalyzed aerobic oxidation and the cleavage/formation of C-S bond are the key steps for this transformation.
- Yuan, Gaoqing,Zheng, Junhua,Gao, Xiaofang,Li, Xianwei,Huang, Liangbin,Chen, Huoji,Jiang, Huanfeng
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supporting information; experimental part
p. 7513 - 7515
(2012/10/07)
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- Polystyrene supported Al(OTf)3: A stable, efficient, selective, and reusable catalyst for sulfonylation of arenes with sulfonic acids
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Cross-linked polystyrene supported aluminium triflate (Ps-Al(OTf) 3) was found to be an efficient and chemoselective heterogeneous Lewis acid catalyst for the direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The solid acid catalyst is stable (as a bench top catalyst) and can be easily recovered and reused without appreciable change in its efficiency.
- Boroujeni, Kaveh Parvanak
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experimental part
p. 1887 - 1890
(2010/11/18)
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- Cross-coupling of organoboronic acids and sulfinate salts using catalytic copper(II) acetate and 1,10-phenanthroline: synthesis of aryl and alkenylsulfones
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A mild method for the preparation of aryl and alkenylsulfones from the cross-coupling reaction of organoboronic acids and sodium sulfinate salts is described. Optimized conditions utilize a catalytic amount of copper(II) acetate monohydrate with 1,10-phenanthroline as ligand in the presence of 4 ? molecular sieves. A co-solvent mixture of dichloromethane/DMSO was used, with reactions occurring at 40 °C under an atmosphere of oxygen. Reaction at room temperature also yields sulfone product, but in lower yields. The method tolerates a variety of substituents on the organoboronic acid, including amide, aldehyde, halide and nitro functionalities, as well as ortho-substituents. In general, the reaction is found to be less efficient using arylboronic acids bearing electron-withdrawing substituents, or using aryltrifluoroborate salts.
- Huang, Fang,Batey, Robert A.
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p. 7667 - 7672
(2008/02/08)
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- Synthesis of aryl sulfones via L-proline-promoted CuI-catalyzed coupling reaction of aryl halides with sulfinic acid salts
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(Chemical Equation Presented) The CuI/L-proline sodium salt catalyzed coupling reaction of aryl halides with sulfinic acid salts readily occurs at 80-95°C in DMSO to give the corresponding aryl sulfones in good to excellent yields. This process is well-tolerated by a wide range of functional groups including hydroxyl, amino, acetanilide, ketone, ester, and nitrile. Using this method, 4-phenylsulfonyl- and 4-methanesulfonyl-substituted L-phenylalanine derivatives are prepared.
- Zhu, Wei,Ma, Dawei
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p. 2696 - 2700
(2007/10/03)
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- Study of regioselective methanesulfonylation of simple aromatics with methanesulfonic anhydride in the presence of zeolite catalysts
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Regioselective methanesulfonylation of simple aromatics using methanesulfonic anhydride can be achieved over zeolite catalysts. For example, methanesulfonylation of toluene over various cation-exchanged zeolite β catalysts affords higher para-selectivity in the synthesis of methyl tolyl sulfone than standard Friedel Crafts methanesulfonylation utilising aluminium chloride.
- Smith, Keith,Ewart, Gordon M.,El-Hiti, Gamal A.,Randles, Kenneth R.
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p. 3150 - 3154
(2007/10/03)
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- A mild and efficient new synthesis of aryl sulfones from boronic acids and sulfinic acid salts
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A new efficient and mild preparation of sulfones from boronic acids and sulfinic acid salts is reported. The cross-coupling reaction mediated by cupric acetate gives access to a variety of sulfones in excellent yield.
- Beaulieu, Christian,Guay, Daniel,Wang, Zhaoyin,Evans, David A.
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p. 3233 - 3236
(2007/10/03)
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- Total Synergistic effect between triflic acid and bismuth(IIIr antimony(III) chlorides in catalysis of the Methanesulfonylation of Arenes
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A total synergistic effect between bismuth(III) or antimony(III) chlorides and triflic acid has been observed in the Friedel-Crafts methanesulfonylation of arenes and has resulted in the development of the first efficient catalytic systems usable for the methanesulfonylation of both activated and deactivated arenes. A proposed mechanism to explain the observed effects is also discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Peyronneau, Magali,Boisdon, Marie-Therese,Roques, Nicolas,Mazieres, Stephane,Le Roux, Christophe
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p. 4636 - 4640
(2007/10/03)
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- An Efficient Copper Catalyst for the Formation of Sulfones from Sulfinic Acid Salts and Aryl Iodides
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(Matrix Presented) A novel copper-catalyzed method for the coupling of sulfinic acid salts and aryl iodides is described. A variety of methyl and diaryl sulfones have been formed in excellent yields.
- Baskin, Jeremy M.,Wang, Zhaoyin
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p. 4423 - 4425
(2007/10/03)
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- Indium-catalysed aryl and alkyl sulfonylation of aromatics
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Commercially available indium (III) triflate is shown to be an extremely efficient catalyst for the sulfonylation of both activated and deactivated aromatics.
- Frost,Hartley,Whittle
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p. 830 - 832
(2007/10/03)
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- Friedel-Crafts sulfonylation of aromatics catalysed by solid acids: An eco-friendly route for sulfone synthesis
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A mild and efficient catalytic method for Friedel-Crafts sulfonylation of arenes to the corresponding sulfones using a catalytic amount of reusable solid acid and arene- or alkanesulfonyl chlorides, sulfonic anhydrides and sulfonic acids as sulfonylating agents is described. Solid acids enable formation of a sulfone by the reaction of a sulfonic acid and an arene for the first time. In pursuit of the development of the best catalytic system, various metal-exchanged K10 montmorillonites and synthetic zeolites such as zeolite beta, zeolite Y and ZSM-5 have been screened for Friedel-Crafts sulfone synthesis. Fe3+-montmorillonite in the family of clays and zeolite beta in the family of zeolites exhibit higher activity. The activity is correlated to the presence of the right mix of Bronsted and Lewis acidic sites. The regioselective sulfonylation of toluene and naphthalene are studied in which para and beta selectivities are observed respectively. The Royal Society of Chemistry 2000.
- Choudary, Boyapati M.,Chowdari, N. Sreenivasa,Kantam, M. Lakshmi
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p. 2689 - 2693
(2007/10/03)
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- Regioselective methanesulfonylation of toluene catalysed by cation-exchanged zeolite β
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The reaction of methanesulfonic anhydride with toluene over various cation exchanged zeolite beta catalysts affords higher para-selectivity and better yields of methyl tolyl sulfone than standard Friedel-Crafts sulfonylation utilising aluminium chloride.
- Smith, Keith,Ewart, Gordon M.,Randles, Kenneth R.
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p. 1085 - 1086
(2007/10/03)
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- Syntheses of o/p-arylthiobenzaldehydes and o/p-methylsulphonylbenzaldehydes
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A general synthesis of o/p-arylthiobenzaldehydes starting from the corresponding chlorobenzaldehydes and an efficient conversion of o/p-methylbenzenethiols to o/p-methylsulphonylbenzaldehydes are described.
- Sivasubramanian, S,Ravichandran, K
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p. 1148 - 1149
(2007/10/02)
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