- Visible-Light-Mediated Late-Stage Sulfonylation of Boronic Acids via N-S Bond Activation of Sulfonamides
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A visible-light-mediated late-stage arylation of N-S bonds in sulfonamides has been developed with using readily available imines as sulfonyl radical source. Diverse complex sulfones could be synthesized by prefunctionalizaiton and subsequent N-S bond ary
- Du, Xian,Li, Yihui,Luo, Yong,Xu, Dejing,Xu, Xiaohong,Xue, Can,Yuan, Han,Zhen, Jingsong
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p. 1986 - 1991
(2022/02/07)
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- A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling
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An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO2 molecule.
- Adenot, Aurélien,Anthore-Dalion, Lucile,Nicolas, Emmanuel,Berthet, Jean-Claude,Thuéry, Pierre,Cantat, Thibault
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supporting information
p. 18047 - 18053
(2021/11/16)
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- Synthesis of Sulfones and Sulfonyl Derivatives using Sodium (tert-butyldimethylsilyl)oxymethanesulfinate
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The present invention relates to a method for manufacturing a sulfone and sulfonyl derivative compound using sodium (tert-butyldimethylsilyl)oxymethanesulfinate, which is a novel organic sulfin salt, wherein the novel organic sulfin salt has good stability, environmental friendliness and economy, and is easy to handle, and thus significantly reduces the amount of transition metal catalysts and the amount of organic sulfin salts used when introducing aryl or alkenyl. Also, alkylation, arylation, amination, and fluorination are all possible during secondary functionalization. Therefore, the present invention can be usefully used in preparation and mass production of various kinds of sulfones and derivatives thereof including asymmetric sulfone derivatives.
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Paragraph 0704-0710; 0712; 0714-0715; 0717-0720; 0757-0760
(2021/04/29)
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- Silyloxymethanesulfinate as a sulfoxylate equivalent for the modular synthesis of sulfones and sulfonyl derivatives
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An efficient protocol for the modular synthesis of sulfones and sulfonyl derivatives has been developed utilizing sodium tert-butyldimethylsilyloxymethanesulfinate (TBSOMS-Na) as a sulfoxylate (SO22-) equivalent. TBSOMS-Na, easily prepared from the commercial reagents Rongalite and TBSCl, serves as a potent nucleophile in S-alkylation and Cu-catalyzed S-arylation reactions with alkyl and aryl electrophiles. The sulfone products thus obtained can undergo the second bond formation at the sulfur center with various electrophiles without a separate unmasking step to afford sulfones and sulfonyl derivatives such as sulfonamides and sulfonyl fluorides.
- Kim, Dae-Kwon,Um, Hyun-Suk,Park, Hoyoon,Kim, Seonwoo,Choi, Jin,Lee, Chulbom
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p. 13071 - 13078
(2021/01/09)
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- Hantzsch Ester as a Visible-Light Photoredox Catalyst for Transition-Metal-Free Coupling of Arylhalides and Arylsulfinates
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Diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (HEH) has been utilized as a visible-light photoredox catalyst for the cross coupling of arylhalides and arylsulfinates without transition metal, sacrificial agent, and mediator. This method is compatible with various functional groups and provides diaryl sulfones in good to high yields. Mechanistic studies indicate that this reaction undergoes the stepwise light irradiation of HE?, single electron transfer (SET) in donor–acceptor complex (DAC) from *HE? to arylhalide, trapping of aryl radical with sulfinate, and SET oxidation of sulfone radical anion by HE. to sulfone by the DAC method.
- Zhu, Da-Liang,Wu, Qi,Li, Hai-Yan,Li, Hong-Xi,Lang, Jian-Ping
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supporting information
p. 3484 - 3488
(2020/03/05)
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- Method for preparing heterocyclic sulfone organic compounds
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The invention discloses a method for preparing heterocyclic sulfone organic compounds from heterocyclic aryl halogen and aryl sulfinate. The method comprises the following steps: 1, in an inert gas protection, according to the molar ratio of heterocyclic aryl halogen compounds, benzene sulfinate compound, inorganic alkali to HEH of 1:2:1.5:0.2, adding the reactants into a reaction container provided with a stirring device, then adding dimethyl sulfoxide, and carrying out stirring reaction for 24 hours at room temperature under blue LED irradiation, so as to obtain the heterocyclic sulfone organic compound. According to the invention, HEH is used as a catalyst for the first time under the condition of not adding any auxiliary transition metal catalyst and precious metal photosensitizer, anda series of cross-coupling reactions of heterocyclic aryl halogen and benzene sulfinate are realized. In addition, the whole process is green, efficient and easy to operate, and the method is excellent for synthesizing the heterocyclic sulfone organic compound.
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Paragraph 0038-0041
(2020/05/08)
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- Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
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Sulfonyl azides have been widely used as sulfonamido, diazo, and azido donors, as well as all-nitrogen 1,3-dipoles donors in synthetic chemistry. Here, the sulfonyl azides were used as efficient sulfonyl donors, which is very unusual. Trifluoromethanesulfonic acid-induced formation of the sulfonyl cation reactive species from sulfonyl azides was developed and used for the first time to couple various inactivated arenes to prepare sulfones at ambient temperature.
- Zhang, Zhiguo,Wang, Songnan,Zhang, Yong,Zhang, Guisheng
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p. 3919 - 3926
(2019/03/29)
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- A practical synthesis of aryl sulfones via cross-coupling of sulfonyl hydrazides with aryltriazenes using copper/ionic liquid combination
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A new and efficient approach adopting copper-catalyzed cross-coupling of sulfonyl hydrazides with aryltriazenes has been developed to synthesize aryl sulfones using Br?nsted acidic ionic liquid as promoter under ambient conditions. The process employs stable and easy to handle reacting partners, and is endowed with broad substrate scope.
- Pandey, Anand Kumar,Kumar, Saurabh,Singh, Rahul,Singh, Krishna Nand
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supporting information
p. 6704 - 6709
(2018/10/15)
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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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- Visible-Light Photoredox/Nickel Dual Catalysis for the Cross-Coupling of Sulfinic Acid Salts with Aryl Iodides
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An efficient cross-coupling of sodium or lithium sulfinates with aryl iodides, using a combination of nickel and photoredox catalysis, is described. The dual catalyst system enables a versatile synthesis of aryl sulfones at room temperature in good yields and displays a broad functional group compatibility. The potential utility of this method in the late-stage diversification of complex molecules and in the conversion of organolithium reagents and sulfur dioxide into sulfones is demonstrated.
- Liu, Nai-Wei,Hofman, Kamil,Herbert, André,Manolikakes, Georg
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supporting information
p. 760 - 763
(2018/02/09)
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- Synthesis of diaryl sulfones at room temperature: Cu-catalyzed cross-coupling of arylsulfonyl chlorides with arylboronic acids
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An efficient and convenient method for the synthesis of diaryl sulfones was developed through the Cu-catalyzed cross-couplings of arylsulfonyl chlorides and arylboronic acids at room temperature in open air. This method is characterized by the use of inexpensive and readily available catalyst and substrates, mild reaction conditions, wide functionality tolerance, short reaction times for most substrates, and moderate to good yields. Stitch it up with copper: An efficient and convenient method for the synthesis of diaryl sulfones was developed through the Cu-catalyzed cross- couplings of arylsulfonyl chlorides and arylboronic acids at room temperature in open air.
- Hu, Feng,Lei, Xiangyang
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p. 1539 - 1542
(2015/05/27)
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- One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts
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A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed.
- Margraf, Natalie,Manolikakes, Georg
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p. 2582 - 2600
(2015/03/18)
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- Arylation of lithium sulfinates with diaryliodonium salts: A direct and versatile access to arylsulfones
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An efficient, transition-metal-free arylation of lithium sulfinates, which are readily accessible from reactions of organolithium reagents with sulfur dioxide, is described. Based on this method, a practical protocol for the direct transformation of (hetero)arenes and (hetero)aromatic halides into diarylsulfones was developed.
- Umierski, Natalie,Manolikakes, Georg
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supporting information
p. 4972 - 4975
(2013/10/22)
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- Metal-free synthesis of diaryl sulfones from arylsulfinic acid salts and diaryliodonium salts
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An efficient, high-yielding, and transition-metal-free synthesis of diaryl sulfones from arylsulfinic acid salts and diaryliodonium salts has been developed. The mild reaction conditions tolerate a range of functional groups, and unsymmetrical diaryliodonium salts show high chemoselectivity.
- Umierski, Natalie,Manolikakes, Georg
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supporting information
p. 188 - 191
(2013/03/28)
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- A mild and efficient synthesis of aryl sulfones from aryl chlorides and sulfinic acid salts using microwave heating
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The CuCl-catalyzed coupling of aryl chlorides and sulfinic acid salts provides a simple and extremely efficient route to unsymmetrical aryl sulfones in high to excellent yields under microwave irradiation within 3-30 minutes. Georg Thieme Verlag Stuttgart · New York.
- Yuan, Yan-Qin,Guo, Sheng-Rong
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supporting information; experimental part
p. 2750 - 2756
(2011/12/04)
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- Anion-functionalized ionic liquids enhance the cui-catalyzed cross-coupling reaction of sulfinic acid salts with aryl halides and vinyl bromides
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An easily accessible, anion-functionalized ionic liquid, 1-ethyl-3-methylimidazolium (S)-2-amino-3-methylbutyric acid salt, [emim][Val], has been demonstrated to be an efficient additive for the CuI-catalyzed coupling reaction of sulfinic acid salts with aryl iodides, aryl bromides and vinyl bromides, leading to the formation of sulfones in good yields. Georg Thieme Verlag Stuttgart.
- Bian, Ming,Xu, Fada,Ma, Cheng
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p. 2951 - 2956
(2008/03/13)
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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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- Unsymmetrical diaryl sulfones through palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides
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A simple and efficient method for the synthesis of unsymmetrical diaryl sulfones using the palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides has been developed. High product yields, a short reaction time, and mild reaction conditions are important features of this method.
- Bandgar,Bettigeri, Sampada V.,Phopase, Jaywant
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p. 2105 - 2108
(2007/10/03)
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- OXIDATIVE SUBSTITUTION XIV. SUBSTITUTION OF HALOGEN IN AROMATIC RING. NEW THEORIES ABOUT THE MECHANISM OF THE ACTION OF CuX2
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The stoichiometry, the comparative reactivity of halogens and hydrogen, the effect of substituents, and the action of an additional oxidizing agent were determined for the reactions of halogenoazulenes with CuX2., leading to substitution of the halogen by the group X (X = Cl, Br, SCN, SeCN, NO2, SO2, Ph).According to model experiments, the equilibrium CuX2 + CuX+ X+ + 2CuX is possible.The reaction of Cu(SO2Ph)2 with Cu(BF4)2 leads to the formation of two equivalents of a copper(I) salt; short-lived particles which substitute the hydrogen and halogen in the substrate are generated during the reaction.It is suggested that the electron generated during oxidation or autooxidation of CuX2 is capable of combining with the substrate.New methods were found for the synthesis of azulene derivatives, and known methods were improved.
- Nefedov, V.A.,Tarygina, L.K.,Kryuchkova, L.V.,Ryabokobylko, Yu.S.
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p. 487 - 499
(2007/10/02)
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