- Dioxygen-Triggered Oxosulfonylation/Sulfonylation of Terminal Olefins toward β-Keto Sulfones/Sulfones
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A dioxygen-triggered oxosulfonylation/sulfonylation of unactivated olefins to achieve β-keto sulfones/sulfones has been developed. Interestingly, pluralistic mechanisms were found when different types of compounds were applied as substrates, and different products were achieved. The reaction is carried out with a high atomic efficiency in the absence of a metal and a catalyst at room temperature under an air atmosphere. Importantly, as a proof-of-concept, a bioactive molecule was synthesized on a gram-scale level using this method.
- Wang, Yanjie,Zhao, Yuhan,Cai, Changqun,Wang, Lingyun,Gong, Hang
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p. 8296 - 8301
(2021/11/13)
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- Copper-Catalyzed Chloro-Arylsulfonylation of Styrene Derivatives via the Insertion of Sulfur Dioxide
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A copper-catalyzed four-component chloro-arylsulfonylation of styrene derivatives with aryldiazonium tetrafluoroborates, lithium chloride, and ex-situ generated sulfur dioxide (from SOgen) is presented. This sulfonylation features good functional group compatibility, mild reaction conditions, excellent regioselectivity, and good yields. The robustness and potential of this method have also been successfully demonstrated by a gram-scale reaction. Based on experimental study, a radical-involved mechanism is proposed for the transformation.
- Li, Yue,Shen, Lin,Zhou, Mi,Xiong, Baojian,Zhang, Xuemei,Lian, Zhong
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supporting information
p. 5880 - 5884
(2021/08/01)
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- Copper-Catalyzed Aerobic Oxidative Cleavage of Unstrained Carbon-Carbon Bonds of 1,1-Disubstituted Alkenes with Sulfonyl Hydrazides
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Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations. However, carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen, is scarce and underdeveloped. Herein, we report alkoxy radical, which was generated from alkyl radical and dioxygen, mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes, providing facile access to a variety of valuable β-keto sulfones. Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselective β-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C—C bond cleavage. Notably, the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.
- Yi, Dong,He, Linying,Qi, Zhongyu,Zhang, Zhijie,Li, Mengshun,Lu, Ji,Wei, Jun,Du, Xi,Fu, Qiang,Wei, Siping
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p. 859 - 865
(2021/03/04)
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- PQS-enabled visible-light iridium photoredox catalysis in water at room temperature
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An amphoteric PQS-attached photocatalyst has been prepared that undergoes self-aggregation in water into nanomicelles. This covalently bound species enables Ir-based photoredox catalysis to be conducted in the absence of additives or co-solvents. Representative reactions are described using this new catalytic system, which require no additional investment of external energy in the form of heating or cooling. The entire aqueous reaction mixture readily undergoes in-flask recycling and thus, represents a sustainable precious metal technology.
- Bu, Mei-Jie,Cai, Chun,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 1233 - 1237
(2018/03/26)
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- Ag-catalyzed sulfonylation-peroxidation of alkenes with sulfonyl hydrazides and T-hydro
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The sulfonylation-peroxidation of alkenes with sulfonyl hydrazides and T-hydro was developed. The Ag-catalyzed three-component peroxidation provides a method for synthesis of a variety of β-sulfonyl peroxides, which could be converted into various sulfone derivatives.
- Xu, Ran,Li, Zhiping
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p. 3942 - 3945
(2018/10/02)
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- Iodine-Triggered Aerobic Oxysulfonylation of Styrenes
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An iodine-triggered dioxygen activation in oxysulfonylation reactions of unactivated olefins using sulfonyl hydrazides and iodine as catalyst is reported here. In one pot, near quantitative syntheses of β-hydroxysulfones were achieved at 70 °C, within 7 h, in acetonitrile and under aerobic conditions. A plausible mechanism is established by radical trapping and 18O labelling experiments for the operationally simple, efficient and economically viable transformation. The direct activation of aerial oxygen under metal-free and mild conditions is proposed for the oxysulfonylation of olefins. (Figure presented.).
- Choudhuri, Khokan,Achar, Tapas Kumar,Mal, Prasenjit
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p. 3566 - 3576
(2017/10/24)
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- One-pot synthesis of β-hydroxysulfones and its application in the preparation of anticancer drug bicalutamide
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An efficient one-pot multistep strategy has been developed, comprising auto-oxidative difunctionalization of alkenes, oxidation of sulfides, and a further reduction of peroxides for the synthesis of complex β-hydroxysulfone derivatives from phenthiols and alkenes. This method has several advantageous characteristics, including readily available substrates, low-cost and environmental benign reagents, nontoxic and renewable solvents, and mild reaction conditions. The application of this transformation to the multigram-scale preparation of the anticancer drug bicalutamide is accomplished.
- Wang, Yajun,Jiang, Wei,Huo, Congde
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p. 10628 - 10634
(2018/05/31)
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- Palladium-mediated synthesis of 1,1,2-triarylethanes. Application to the synthesis of CDP-840
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A three-step protocol toward 1,1,2-triarylethanes 1 starting with β-ketosulfones 2 is developed. A facile process is carried out for the (1) reduction of 2 with NaBH4, (2) BF3·OEt2-mediated Friedel-Crafts reactions of the
- Lin, Yi-Shan,Kuo, Yi-Chun,Kuei, Chun-Hsiung,Chang, Meng-Yang
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p. 1275 - 1282
(2017/02/10)
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- Synthesis of γ-sulfonyl δ-lactones and β-sulfonyl styrenes
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A facile route to the synthesis of γ-sulfonyl lactones 5 and β-sulfonyl styrenes 6 has been developed, achieving moderate to good yields via the (1) NaH mediated Michael addition of β-ketosulfones 3 and methyl acrylate in refluxing THF and (2) NaBH4mediated stereoselective reduction/lactonization of δ-ketoesters 4 in boiling MeOH, or (3) boron trifluoride etherate mediated ring-opening of lactones 5 in MeOH at reflux.
- Chan, Chieh-Kai,Chen, Yu-Hsin,Hsu, Ru-Ting,Chang, Meng-Yang
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- An Efficient Organic Electrosynthesis of β-Hydroxysulfones
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An efficient organic electrosynthesis of tertiary β-hydroxysulfones from functionalized α-methylstyrenes with substituted sodium sulfinates has been established. The novel electrosynthetic method provided the desired products in excellent yields, and the key structure was confirmed by X-ray single-crystal diffraction analysis.
- Chan, Chieh-Kai,Lo, Nai-Chang,Chen, Po-Yu,Chang, Meng-Yang
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p. 4469 - 4477
(2017/09/26)
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- Copper(i)-mediated synthesis of β-hydroxysulfones from styrenes and sulfonylhydrazides: An electrochemical mechanistic study
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Copper(i) halides were used as mediators in the synthesis of β-hydroxysulfones via the oxysulfonylation of styrenes using sulfonylhydrazides. The feature of the developed process lies in the combination of a copper(i) salt with oxygen - the stoichiometric oxidant. Copper(ii) species are responsible for the oxidation of sulfonylhydrazides, they are generated in small amounts in the O2/Cu(i)/Cu(ii) redox system, which is formed during the reaction. The combination of these three components enables one to obtain in the case of α-methylstyrenes only β-hydroxysulfones and in the case of α-unsubstituted styrenes, β-hydroxysulfones as the main products and β-ketosulfones as the by-products. With good yields β-hydroxysulfones were prepared by reduction of the reaction mixture containing both products β-hydroxysulfones and β-ketosulfones with NaBH4. An electrochemical study revealed that the Cu(i)/Cu(II) pair can serve as an effective mediator of β-hydroxysulfones formation via redox processes.
- Terent'Ev, Alexander O.,Mulina, Olga M.,Pirgach, Dmitry A.,Demchuk, Dmitry V.,Syroeshkin, Mikhail A.,Nikishin, Gennady I.
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p. 93476 - 93485
(2016/10/17)
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- Synthesis of β-Hydroxysulfones from Sulfonyl Chlorides and Alkenes Utilizing Visible Light Photocatalytic Sequences
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The synthesis of β-hydroxysulfones from sulfonyl chlorides and styrenes in the presence of water by a visible light mediated atom transfer radical addition (ATRA)-like process utilizing fac[Ir(ppy)3] as photoredox catalyst was developed in high
- Pagire, Santosh K.,Paria, Suva,Reiser, Oliver
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supporting information
p. 2106 - 2109
(2016/06/01)
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- A convenient access to β-iodo sulfone by the iodine-mediated iodosulfonylation of alkenes
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A novel iodine-mediated intermolecular iodosulfonylation reaction of alkenes for dual C-S and C-I bond formation is described. A series of alkenes could be selectively converted into the corresponding β-iodo sulfones, which are versatile building blocks in organic synthesis and medicinal chemistry. Molecular iodine was the iodine source in this reaction.
- Sun, Kai,Lv, Yunhe,Zhu, Zhonghong,Jiang, Yongqing,Qi, Jiejie,Wu, Hankui,Zhang, Zhiguo,Zhang, Guisheng,Wang, Xin
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p. 50701 - 50704
(2015/06/25)
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- Aerobic Nickel-Catalyzed Hydroxysulfonylation of Alkenes Using Sodium Sulfinates
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Nickel-catalyzed hydroxysulfonylation of alkenes was achieved using sodium sulfinates under air atmosphere. The procedure enabled the selective synthesis of β-hydroxysulfones in good yields and suppressed the formation of β-ketosulfones. On the contrary, sulfonylation of alkynes with sodium sulfonates afforded only β-ketosulfones.
- Taniguchi, Nobukazu
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p. 7797 - 7802
(2015/08/18)
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- Regioselectivity of vinyl sulfone based 1,3-dipolar cycloaddition reactions with sugar azides by computational and experimental studies
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DFT (M06-L) calculations on the transition state for the 1,3-dipolar cycloadditions between substituted vinyl sulfones with sugar azide have been reported in conjunction with new experimental results, and the origin of reversal of regioselectivity has been revealed using a distortion/interaction model. This study provides the scientific justification for combining organic azides with two different types of vinyl sulfones for the preparation of 1,5-disubstituted 1,2,3-triazoles and 1,4-disubstituted triazolyl esters under metal-free conditions.
- Sahu, Debashis,Dey, Santu,Pathak, Tanmaya,Ganguly, Bishwajit
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supporting information
p. 2100 - 2103
(2014/05/06)
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- Molecular-iodine-catalyzed aerobic oxidative synthesis of β-hydroxy sulfones from alkenes
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The synthesis of β-hydroxy sulfones from alkenes and sodium sulfinates under aerobic oxidative conditions was achieved in the presence of a catalytic amount of molecular iodine. Molecular oxygen in air serves as the terminal oxidant and the catalytic amount of molecular iodine acts as the sulfonyl radical initiator and peroxide reductant. This journal is the Partner Organisations 2014.
- Kariya, Atsumasa,Yamaguchi, Tomoaki,Nobuta, Tomoya,Tada, Norihiro,Miura, Tsuyoshi,Itoh, Akichika
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p. 12191 - 12194
(2014/04/03)
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- Copper-catalyzed direct oxysulfonylation of alkenes with dioxygen and sulfonylhydrazides leading to β-ketosulfones
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The first copper-catalyzed oxysulfonylation reaction of alkenes with dioxygen and sulfonylhydrazides for the construction of β-ketosulfones has been developed under mild conditions without any ligand or additive.
- Wei, Wei,Liu, Chunli,Yang, Daoshan,Wen, Jiangwei,You, Jinmao,Suo, Yourui,Wang, Hua
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supporting information
p. 10239 - 10241
(2013/10/22)
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- Aerobic oxysulfonylation of alkenes leading to secondary and tertiary β-hydroxysulfones
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New channel! A novel and attractive dioxygen activation by sulfinic acids was explored that is capable of performing efficiently without the assistance of transition metals or radical initiators. This reaction furnishes secondary and tertiary β-hydroxysulfones under mild conditions; β-hydroperoxysulfone was isolated as an important intermediate. Copyright
- Lu, Qingquan,Zhang, Jian,Wei, Fuliang,Qi, Yue,Wang, Huamin,Liu, Zhiliang,Lei, Aiwen
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supporting information
p. 7156 - 7159
(2013/07/26)
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- A one-pot regioselective synthetic route to vinyl sulfones from terminal epoxides in aqueous media
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A highly efficient LiBr catalysed regioselective synthesis of vinyl sulfones from readily available terminal epoxides and sodium sulfinates in a one-pot procedure using water as a reaction medium is reported. The protocol is adorned with several attributes of green chemistry like recycling of the catalyst, atom-economy and an aqueous medium.
- Chawla, Ruchi,Kapoor, Ritu,Singh, Atul K.,Yadav, Lal Dhar S.
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scheme or table
p. 1308 - 1313
(2012/06/01)
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- Stereoselective synthesis of (E)-alkenyl sulfones from alkenes or alkynes via copper-catalyzed oxidation of sodium sulfinates
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Alkenyl sulfones can be stereoselectively synthesized from alkenes or alkynes using sodium sulfinates. The reaction can be performed by a copper-catalyzed oxidation of sodium sulfinates in air. The reaction of alkenes gives (E)-alkenyl sulfones via anti addition of sulfonyl cation and elimination process. Furthermore, the employment of alkynes produces (E) β- haloalkenyl sulfones in the presence of potassium halides. Georg Thieme Verlag Stuttgart · New York.
- Taniguchi, Nobukazu
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scheme or table
p. 1308 - 1312
(2011/07/07)
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- Iron-catalyzed sulfonyl radical formations from sulfonylhydrazides and oxidative addition to alkenes
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Generation of sulfonyl radicals from sulfonylhydrazides has been achieved in the presence of a non-toxic iron catalyst and oxygen. The intermolecular addition of resultant sulfonyl radicals to alkenes affords β-hydroxysulfone compounds.
- Taniguchi, Tsuyoshi,Idota, Atsushi,Ishibashi, Hiroyuki
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experimental part
p. 3151 - 3153
(2011/05/12)
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- An approach toward the synthesis of β-hydroxy sulfones on water
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Various β-hydroxyl sulfones are prepared by regioselective ring opening of epoxides with sodium salt of sulfinate on water. This is an efficient protocol which avoids hazardous and moisture sensitive catalysts.
- Narayana Murthy,Madhav,Prakash Reddy,Rama Rao,Nageswar
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scheme or table
p. 5009 - 5011
(2009/12/01)
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- Acid-promoted reaction of sulfonyl chlorides with alkenes: New approach to the regioselective synthesis of β-hydroxyl sulfone derivatives
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Reaction of sulfonyl chlorides with alkenes and water in the presence of catalytic amount of sulfonic acid provided β-hydroxyl sulfone derivatives in high yields.
- Xi, Chanjuan,Lai, Chunbo,Chen, Chao,Wang, Ruji
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p. 1595 - 1597
(2007/10/03)
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- Simple synthesis of β-hydroxysulfones using polysorbate-80 as phase transfer catalyst
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A very easy and practical method for the preparation of β-hydroxysulfones has been developed by ring opening of oxirane using polysorbate-80 as phase transfer catalyst.
- Maiti, A. K.,Bhattacharyya, P.
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- Polyethylene Glycol (PEG) 4000 Catalysed Regioselective Nucleophilic Ring Opening of Oxiranes - A New And Convenient Synthesis of β-Hydroxy Sulfone and β-Hydroxy Sulfide
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Oxiranes and sodium p-toluene sulfinate salt react smoothly in a regioselective manner in the presence of PEG4000 to furnish β-hydroxy sulfone and β-hydroxysulfide.The reaction was extended for the preparation of alkylsulfones and β-oxosulfones from alkylhalide and β-oxohalide respectively.
- Maiti, A. K.,Bhattacharyya, P.
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p. 10483 - 10490
(2007/10/02)
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- Regioselective ring opening of oxiranes catalysed by montmorillonite clay: A simple synthesis of β-hydroxy sulfones
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Oxiranes and sodium p-toluene sulfinate salt react smoothly in a regioselective manner in the presence of montmorillonite clay to furnish the corresponding β-hydroxy sulfones in good to excellent yield.
- Biswas,Bhattacharyya
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p. 569 - 573
(2007/10/02)
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