- Metal-Free Aminomethylation of Aromatic Sulfones Promoted by Eosin Y
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A metal-free α-aminomethylation of heteroaryls promoted by eosin Y under green light irradiation is reported. A large variety of α-trimethylsilylamines as precursor of α-aminomethyl radical species were engaged to functionalize sulfonyl-heteroaryls following a Homolytic Aromatic Substitution (HAS) pathway. This method has provided a range of α-aminoheteroaryl compounds including a functionalized natural product. The mechanism of this late-stage functionalization of aryls was investigated and suggests the formation of a sulfonyl radical intermediate over a reductive quenching cycle.
- Thierry, Thibault,Pfund, Emmanuel,Lequeux, Thierry
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supporting information
p. 14826 - 14830
(2021/10/01)
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- Ball-milling synthesis of sulfonyl quinolines: Via coupling of haloquinolines with sulfonic acids
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An efficient and practical approach for the synthesis of sulfonyl quinolines via ball milling promoted coupling of haloquinolines with sulfonic acid under metal-, solvent- and additive-free conditions has been developed. In contrast to the solvent-based s
- Liu, Xiao-Wen,Ma, Hui,Wang, Jia-Qian,Xie, Long-Yong,Zhu, Qi
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supporting information
p. 7589 - 7593
(2021/10/12)
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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 0034-0037; 0046-0049
(2020/05/08)
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- SO2F2-mediated deoxygenative C2-sulfonylation of quinoline N-oxides with sodium sulfinates
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A mild and efficient method for deoxygenative C2-sulfonylation of quinoline N-Oxides in the presence of a base has been developed employing extremely inexpensive SO2F2 as an activator and sodium sulfinate as nucleophilic sulfonylation source. It is noteworthy that the reaction proceeded well under metal- and oxidant-free conditions to give a variety of 2-sulfonylquinolines in medium to good yields.
- Ai, Chengmei,Liao, Xudong,Zhou, Yi,Yan, Zhaohua,Lin, Sen
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supporting information
(2020/12/07)
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- Copper-Catalyzed Deoxygenative C2-Sulfonylation of Quinoline N -Oxides with DABSO and Phenyldiazonium Tetrafluoroborates for the Synthesis of 2-Sulfonylquinolines via a Radical Reaction
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An efficient and practical method for the synthesis of 2-sulfonylquinolines through copper-catalyzed deoxygenative C2-sulfonylation of quinoline N -oxides with 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO) and phenyldiazonium tetrafluoroborates is demonstrated. Products with various substituents were obtained in moderate to high yields.
- Deng, Qi,Dong, Dao-Qing,Li, Guang-Hui,Wang, Zu-Li,Yan, Shi-Qiang
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p. 3313 - 3319
(2019/08/28)
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- Transition-metal- and oxidant-free three-component reaction of quinoline: N -oxides, sodium metabisulfite and aryldiazonium tetrafluoroborates via a dual radical coupling process
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A convenient and straightforward three-component transformation of quinoline N-oxides, sodium metabisulfite and aryldiazonium tetrafluoroborates has been developed, providing the target products in moderate to good yields. Compared with previous studies, the present methodology avoids the use of transition-metal catalysts and excess oxidants, providing a simple and practical alternative approach for the construction of 2-sulfonylquinolines. Control experiments indicate that a dual radical coupling process is responsible for this reaction.
- You, Guirong,Xi, Dan,Sun, Jian,Hao, Liqiang,Xia, Chengcai
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p. 9479 - 9488
(2019/11/14)
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- Visible-light-induced deoxygenative C2-sulfonylation of quinoline N-oxides with sulfinic acids for the synthesis of 2-sulfonylquinoline via radical reactions
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A simple and efficient method for the synthesis of 2-sulfonylquinoline from deoxygenative C2-sulfonylation of quinoline N-oxides with sulfinic acid induced by visible light is presented. This protocol shows a broad substrate scope, and desired products wi
- Dong, Dao-Qing,Li, Li-Xia,Li, Guang-Hui,Deng, Qi,Wang, Zu-Li,Long, Shu
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p. 1494 - 1498
(2019/09/09)
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- Visible-light-induced deoxygenative C2-sulfonylation of quinoline: N -oxides with sulfinic acids
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The first example of visible-light-induced deoxygenative C2-sulfonylation of quinoline N-oxides with sulfinic acids in the presence of an organic dye as the catalyst was developed. The reaction conditions are eco-friendly and mild, employing ambient air as the sole oxidant and aqueous acetone solution as the solvent. This approach requires only a very low catalyst loading, allowing gram-scale preparation as well as late-stage modification of biologically active compounds bearing quinoline groups.
- Xie, Long-Yong,Fang, Tai-Gang,Tan, Jia-Xi,Zhang, Bo,Cao, Zhong,Yang, Li-Hua,He, Wei-Min
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supporting information
p. 3858 - 3863
(2019/07/31)
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- Direct coupling of haloquinolines and sulfonyl chlorides leading to sulfonylated quinolines in water
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A simple and efficient method has been developed for construction of sulfonylated quinolines via coupling of haloquinolines and sulfonyl chlorides in water. The present methodology provides an attractive approach to various sulfonylated quinolines in moderate to good yields with favorable functional group tolerance, which has the advantages of operation simplicity, readily available starting materials, excellent regioselectivity, scale-up synthesis, and organic solvent-free conditions.
- Bao, Pengli,Wang, Leilei,Liu, Qishun,Yang, Daoshan,Wang, Hua,Zhao, Xiaohui,Yue, Huilan,Wei, Wei
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supporting information
p. 214 - 218
(2019/01/04)
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- TsCl-promoted sulfonylation of quinoline N-oxides with sodium sulfinates in water
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An eco-friendly protocol for the synthesis of various 2-sulfonyl quinolines/pyridines through sulfonylation of heteroaromatic N-oxides with sodium sulfinates in water at ambient temperature under metal- and oxidant-free conditions has been developed. The mild reaction conditions, high reaction efficiency, operational simplicity, short reaction time and remarkable functional-group compatibility make the developed protocol very attractive for the preparation of 2-sulfonyl N-heteroaromatic compounds.
- Peng, Sha,Song, Yan-Xi,He, Jun-Yi,Tang, Shan-Shan,Tan, Jia-Xi,Cao, Zhong,Lin, Ying-Wu,He, Wei-Min
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p. 2287 - 2290
(2019/09/04)
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- Exogenous-oxidant-and catalyst-free electrochemical deoxygenative C2 sulfonylation of quinoline: N-oxides
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An exogenous-oxidant-and catalyst-free electrochemical deoxygenative C2 sulfonylation reaction has been achieved. By employing quinoline N-oxides as the starting materials, the electrochemical C-H sulfonylation of electron-deficient quinolines was indirectly achieved at room temperature and a variety of sulfonylated quinoline derivatives were synthesized in modest to high yield with excellent regioselectivity. Notably, this protocol is the first example for synthesizing sulfonylated electron-deficient heteroarenes/arenes through electrochemistry.
- Jiang, Minbao,Yuan, Yong,Wang, Tao,Xiong, Yunkui,Li, Jun,Guo, Huijiao,Lei, Aiwen
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p. 13852 - 13855
(2019/11/21)
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- Metal-free catalyzed arylsulfonylation of chloroquinoline with sodium arylsulfinates under microwave irradiation
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An efficient protocol for the synthesis of 2-arylsulfonyl quinolines has been developed via a metal-free catalyzed cross-coupling reaction of chloroquinoline with sodium arylsulfinates in moderate-to-good yields under microwave irradiation. The reactions proceed with a wide range of substrates with good functional group tolerance.
- Li, Xi-Yong,Sun, Ya-Min,Yuan, Jin-Wei
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p. 295 - 303
(2018/05/03)
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- Intramolecular Desulfitative Coupling: Nickel-Catalyzed Transformation of Diaryl Sulfones into Biaryls via Extrusion of SO2
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As a new transformation of organosulfur compounds, intramolecular desulfitative coupling of diaryl sulfones to the corresponding biaryls has been developed with the aid of nickel-NHC catalysts. This catalytic elimination of SO2 was also applicable to alkenyl aryl sulfone to furnish the corresponding alkenyl arene.
- Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 6601 - 6605
(2018/10/20)
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- Synthetic method of 2-arylsulfonyl quinoline derivatives
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The invention discloses a synthetic method of 2-arylsulfonyl quinoline derivatives. 2-halo-quinoline compounds, aryl sulfonyl chloride compounds and sulfite are subjected to one-pot reaction in an aqueous solution under ultrasonication, and the 2-arylsulfonyl quinoline derivatives are synthesized. The method has the advantages of easily available raw materials, simple, mild, green and energy-saving reaction conditions, high reaction selectivity and yield and excellent compatibility of substrate functional groups; the 2-arylsulfonyl quinoline derivatives can be particularly obtained by filtering and direct separation, so that production cost is reduced, the problem of environmental pollution caused by the traditional method is solved, and the method is environmentally friendly and has higher application value.
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Paragraph 0078; 0079; 0080; 0081
(2019/01/14)
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- Iron-catalyzed deoxygenation and 2-sulfonylation of quinoline N-oxides by sodium sulfinates towards 2-sulfonyl quinolines
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An iron(III)-catalyzed protocol towards 2-sulfonyl quinolines from quinoline N-oxides and sodium sulfinates was herein illustrated. The general and direct option featured for high efficiency (up to 91% yields) and good functional compatibilities (27 examples) in the Fe(III)-catalysis. Moreover, free radical mechanism was proposed for the one-pot deoxygenation and sulfonylation reaction based on the results of the control reactions.
- Li, Ping,Jiang, Yangji,Li, Han,Dong, Wanrong,Peng, Zhihong,An, Delie
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supporting information
p. 1909 - 1918
(2018/07/21)
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- Iodine/TBHP-Promoted One-Pot Deoxygenation and Direct 2-Sulfonylation of Quinoline N-Oxides with Sodium Sulfinates: Facile and Regioselective Synthesis of 2-Sulfonylquinolines
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A highly efficient iodine/TBHP-mediated one-pot deoxygenative and regioselective 2-sulfonylation of quinoline N-oxides with sodium sulfinate salts has been developed. This metal-, base-, and phosphorus-free protocol employs readily accessible and easy-to-handle reagents and can be conveniently carried out at room temperature under mild conditions, providing an alternative access to a series of 2-sulfonylquinolines and other related heteroaryl sulfone products in moderate-to-excellent yields within a short reaction time.
- Sumunnee, Ladawan,Buathongjan, Chonchanok,Pimpasri, Chaleena,Yotphan, Sirilata
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p. 1025 - 1032
(2017/02/15)
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- Iron-catalysed regioselective arylsulfonylation of quinoline N-oxides with sodium arylsulfinates under microwave irradiation
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An efficient protocol for one-pot deoxygenative and regioselective synthesis of 2-arylsulfonylquinolines has been developed via ironcatalysed cross-coupling reaction of quinoline N-oxides with sodium arylsulfinates in moderate to good yields under microwave irradiation. The reactions proceeded over a broad range of substrates with good regioselectivity and functional group tolerance.
- Mai, Wenpeng,Lv, Mingxiu,Zhang, Xiaofeng,Lu, Kui
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p. 705 - 708
(2018/01/08)
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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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p. 4144 - 4147
(2016/08/30)
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- In Situ Generated HypoIodite Activator for the C2 Sulfonylation of Heteroaromatic N-oxides
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A mild approach for direct C2 sulfonylation of heteroaromatic N-oxides with sulfonyl hydrazides affording 2-sulfonyl quinolines/pyridines has been developed. A variety of heteroaromatic N-oxides and sulfonyl hydrazides participate effectively in this transformation which uses hypoiodites (generated in situ from NaI and TBHP) as a means of substrate activators. In this reaction, the N-oxide plays a dual role, acting as a traceless directing group as well as a source of oxygen atom.
- Su, Yuan,Zhou, Xuejun,He, Chunlian,Zhang, Wei,Ling, Xiao,Xiao, Xia
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p. 4981 - 4987
(2016/07/06)
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- H-phosphonate-mediated sulfonylation of heteroaromatic N-oxides: a mild and metal-free one-pot synthesis of 2-sulfonyl quinolines/pyridines
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A smart H-phosphonate-mediated synthetic strategy for the sulfonylation of heteroaromatic N-oxides has been developed, by which a large variety of 2-sulfonyl quinolines/pyridines were synthesized starting from easily available sulfonyl chlorides, diisopropyl H-phosphonate and pyridine/quinoline N-oxides in one pot under metal-free conditions at room temperature.
- Sun, Kai,Chen, Xiao-Lan,Li, Xu,Qu, Ling-Bo,Bi, Wen-Zhu,Chen, Xi,Ma, Hui-Li,Zhang, Song-Tao,Han, Bo-Wen,Zhao, Yu-Fen,Li, Chao-Jun
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supporting information
p. 12111 - 12114
(2015/07/28)
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- Green chemical synthesis of 2-benzenesulfonyl-pyridine and related derivatives
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A practical synthesis of 2-benzenesulfonylpyridine, 1, is described which is a key starting material for the manufacture of an investigational new drug candidate at Eli Lilly and Company. An optimized green chemical process was developed which features a novel tandem SNAr/oxidation under mild conditions to produce the target sulfone, 1, in 86% yield and>99% purity. In addition, this novel, environmentally friendly methodology was found to be general for the synthesis of substituted aromatic pyridyl sulfides and sulfones.
- Trankle, William G.,Kopach, Michael E.
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supporting information
p. 913 - 917
(2012/12/30)
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