- Synthesis of Sulfonated Benzo[d][1,3]oxazines by Merging Photoredox Catalysis and Insertion of Sulfur Dioxide
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A photocatalytic reaction of N-(2-vinylphenyl)amides, DABCO?(SO2)2 and arenediazonium tetrafluoroborates for the synthesis of 4-((arylsulfonyl)methyl)-4H-benzo[d][1,3]oxazines under mild conditions is reported. This synthetic approac
- Liu, Tong,Zheng, Danqing,Li, Zhenhua,Wu, Jie
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- Generation of Sulfonyl Radicals from Aryldiazonium Tetrafluoroborates and Sulfur Dioxide: The Synthesis of 3-Sulfonated Coumarins
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A catalyst-free approach for the generation of sulfonyl radicals from aryldiazonium tetrafluoroborates in the presence of DABCO?(SO2)2is realized. The combination of aryldiazonium tetrafluoroborates, DABCO?(SO2)2, and aryl propiolates affords 3-sulfonated coumarins in good to excellent yields. This tandem reaction process involves radical addition, spirocyclization, and 1,2-migration of esters. Additionally, the in situ diazotization of a number of anilines allows the directional synthesis of desired 3-sulfonated coumarins in a one-pot, two-step process.
- Zheng, Danqing,Yu, Jiyao,Wu, Jie
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- Metal-Free Visible-Light Photocatalytic Tandem Radical Addition–Cyclization Strategy for the Synthesis of Sulfonyl-Containing Isoquinolinediones
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A mild radical cascade reaction for the synthesis of sulfonyl-containing isoquinolinediones has been developed, in which sulfonyl radicals can be accessed from simple sodium sulfinates under visible light and eosin Y catalysis. This tandem approach features a broad range of substrates and functional group tolerance. With this strategy, trifluoromethylated isoquinolinedione was also obtained.
- Zuo, Kai-Li,He, Yan-Hong,Guan, Zhi
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- Nickel-Catalyzed Intermolecular Carbosulfonylation of Alkynes via Sulfonyl Radicals
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β,β-Disubstituted vinyl sulfones were obtained with complete regio- and stereocontrol in a multicomponent reaction involving alkynes, organoboronic acids, and sulfonyl chlorides in the presence of a nickel catalyst. The reaction proceeds via sulfonyl radicals generated in situ under mild reaction conditions.
- García-Domínguez, Andrés,Müller, Simona,Nevado, Cristina
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- HUSY zeolite promoted hydrophenylation of alkynes conjugated with electron-withdrawing substituents
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Arylacetylenes, conjugated with electron-withdrawing groups, ArC[tbnd6]C(EWG) [EWG = SO2Ph, PO(OEt)2, COMe, CO2Me] in reaction with benzene at room temperature or 130?°C (glass high pressure tube) for 1–10?h under the acti
- Ryabukhin, Dmitry S.,Vasilyev, Aleksander V.
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- MOF-Derived Subnanometer Cobalt Catalyst for Selective C-H Oxidative Sulfonylation of Tetrahydroquinoxalines with Sodium Sulfinates
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The development and utilization of reusable base-metal catalysts is a central topic in catalysis. Herein, via a catalyst design strategy, we present the preparation of a highly dispersed and acid-resistant subnanometer cobalt catalyst (1 nm) by a MOF-templated method, which has been utilized for selective C-H oxidative sulfonylation of tetrahydroquinoxalines with odorless sodium sulfinates. The transformation enables generation of a variety of sulfonylquinoxalines with the merits of good substrate and functional group compatibility, high regio- and chemoselectivity, and the use of a naturally abundant and reusable metal catalyst. The work presented offers the potential for further design of heterogeneous nanocatalysts and fabrication of functional products that are difficult to prepare or inaccessible by homogeneous catalysis.
- Xie, Feng,Lu, Guang-Peng,Xie, Rong,Chen, Qing-Hua,Jiang, Huan-Feng,Zhang, Min
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- Light-Mediated Difluoromethylthiolation of Aldehydes with a Hydrogen Atom Transfer Photocatalyst
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A mild general method for difluoromethylthiolation of aldehydes with PhSO2SCF2H and a decatungstate photocatalyst under redox-neutral conditions has been developed. This reaction is highly efficient, scalable, and oxidant-free. The broad substrate scope and excellent functional group tolerance of the reaction make it suitable for generating libraries of difluoromethyl thioesters. We demonstrated the utility and sustainability of the method by synthesizing several structurally complex difluoromethyl thioesters.
- Dong, Jianyang,Yue, Fuyang,Wang, Xiaochen,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
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- An efficient transition metal-free difunctionalization of alkenes in water for the green preparation of sulfone compounds
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A direct difunctionalization method of alkenes with quinoxalin-2(1H)-ones and sodium sulfonates toward sulfone derivatives has been developed under environmentally friendly conditions. This strategy represents an efficient and practical difunctionalization of olefins using water/aqueous media as a sustainable solvent. In addition, this transition metal-free reaction is high yield, and operationally simple, and in particular, proceeds under mild conditions to afford desired sulfones with high functional group compatibility.
- Yang, Guang,Wang, Shoucai,Nie, Hongsheng,Xiong, Zhicheng,Li, Xuan,Ji, Fanghua,Jiang, Guangbin
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- Electrochemistry Enabled Nickel-Catalyzed Selective C?S Bond Coupling Reaction
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This work describes an electrochemical enabled nickel-catalyzed chemoselective C?S bond coupling protocol for the production of aryl sulfides and sulfones. By simply switching the nickel catalysts and electrodes, this electrochemical C?S bond coupling has demonstrated excellent redox activity, scalability and sustainability. Furthermore, the mechanism for this electrochemical cross-coupling reaction has been investigated.
- Pan, Yi,Wang, Yang,Wang, Yi,Zhang, Feng
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- Sodium iodide-mediated synthesis of vinyl sulfides and vinyl sulfones with solvent-controlled chemical selectivity
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Vinyl sulfides and vinyl sulfones are ubiquitous structures in organic chemistry because of their presence in natural and biologically active compounds and are very frequently encountered structural motifs in organic synthesis. Herein we report an efficie
- Liu, Congrong,Wu, Gongde,Xu, Jin
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p. 35156 - 35160
(2021/11/30)
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- Visible-Light-Triggered Sulfonylation/Aryl Migration/Desulfonylation and C-S/Se Bond Formation Reaction: 1,2,4-Trifunctionalization of Butenyl Benzothiazole Sulfone with Thiosulfonate/Selenosulfonates
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A visible-light-triggered radical cascade sulfonylation/aryl migration/desulfonylation and C-S/Se bond formation reaction of butenyl benzothiazole sulfone with thiosulfonates or selenosulfonates is developed. This study affords the 1,2,4-trifunctionalization of butenyl benzothiazole sulfone derivatives under mild conditions.
- Liu, Xin-Yu,Tian, Shi-Yin,Jiang, Yi-Fan,Rao, Weidong,Wang, Shun-Yi
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supporting information
p. 8246 - 8251
(2021/11/01)
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- Electrochemical sulfonylation of enamides with sodium sulfinates to access β-amidovinyl sulfones
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The electrochemical sulfonylation of enamides with sodium sulfinates was developed in an undivided cell in constant current mode, leading to the formation of β-amidovinyl sulfones in moderate to good yields. The catalyst-, electrolyte- and oxidant-free protocol features good functional group tolerance and employs electric current as a green oxidant. Mechanistic insights into the reaction indicate that the reaction may proceedviaa radical mechanism.
- Gu, Qingyun,Liu, Xinyi,Shao, Yu,Wang, Xin,Wu, Guixia,Xie, Yushan,Zeng, Xiaobao,Zhao, Yu
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supporting information
p. 8295 - 8300
(2021/10/14)
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- Difluoroaminosulfonylation of Styrenes with N,N-Difluorobenzenesulfonamide
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A new type of difluoroaminosulfonylation of styrenes with N,N-difluorobenzenesulfonamide (DFBSA) was developed, using NiCl2/Mn as catalysts and bipyridine as the ligand, to afford a series of 1-difluoroamino-2-phenylsulfonyl products. Preliminary mechanistic studies proved a free radical process for the reaction.
- Yang, Xianjin,Zhang, Wenqing
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- Iron-Catalyzed, Site-Selective Difluoromethylthiolation (-SCF2H) and Difluoromethylselenation (-SeCF2H) of Unactivated C(sp3)-H Bonds in N-Fluoroamides
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The iron-catalyzed δ-C(sp3)-H bond difluoromethylthiolation and difluoromethylselenation of aliphatic amides with high site selectivity are reported. Essential to the success is the employment of an amide radical formed in situ to activate the inert C(sp3
- Zhang, Hongwei,Yu, Fei,Li, Chuang,Tian, Peiyuan,Zhou, Yulu,Cao, Zhong-Yan
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supporting information
p. 4721 - 4725
(2021/06/28)
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- Synthesis of (E)-iodo vinylsulfones via oxidative addition of thiol into alkyne under metal free condition
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An efficient, transition-metal free and molecular iodine promoted protocol for the construction of (E)-β-iodovinyl sulfone derivatives via oxidative C–S coupling of thiol and alkyne has been demonstrated. Both aryl and alkyl terminal acetylenes were found to be an excellent substrate for the present reaction which provides a wide range of β-iodovinyl sulfone derivatives with very good yield and excellent regio and stereo-selectivities. Diaryldisulfide is also found to be an equally efficient sulfonyl group surrogate under identical reaction conditions.
- Samanta, Surya Kanta,Sarkar, Rumpa,Bera, Mrinal K.
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- One-Pot Synthesis of Pentafluorophenyl Sulfonic Esters via Copper-Catalyzed Reaction of Aryl Diazonium Salts, DABSO, and Pentafluorophenol
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Pentafluorophenyl (PFP) sulfonic esters were synthesized via a copper-catalyzed one-pot multicomponent reaction of aryl diazonium tetrafluoroborate, DABSO (DABCO·(SO2)2), and pentafluorophenol. The reaction system provided the desired pentafluorophenyl sulfonic esters in good yields and exhibited excellent functional group tolerance. In addition, the generated PFP sulfonic esters were successfully applied in Sonogashira, Suzuki, Chan-Evans-Lam, and decarboxylative coupling reactions.
- Idris, Muhammad Aliyu,Lee, Sunwoo
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supporting information
p. 4516 - 4520
(2021/05/26)
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- Visible-Light-Mediated Alkenylation of Alkyl Boronic Acids without an External Lewis Base as an Activator
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Herein we report a protocol for the direct visible-light-mediated alkenylation of alkyl boronic acids at room temperature without an external Lewis base as an activator, and we propose a mechanism involving benzenesulfinate activation of the alkyl boronic acids. The protocol permits the efficient functionalization of a broad range of cyclic and acyclic primary and secondary alkyl boronic acids with various alkenyl sulfones. We demonstrated its utility by preparing or functionalizing several pharmaceuticals and natural products.
- Yue, Fuyang,Dong, Jianyang,Liu, Yuxiu,Wang, Qingmin
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supporting information
p. 2477 - 2481
(2021/04/05)
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- Visible-light-mediated alkylation of 4-alkyl-1,4-dihydropyridines with alkenyl sulfones
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Herein we report a mild, general protocol for visible-light-mediated alkylation of 4-alkyl-1,4-dihydropyridines with alkenyl sulfones. The protocol permits efficient functionalization of sulfones with a broad range of cyclic and acyclic secondary and tert
- Dong, Jianyang,Liu, Yuxiu,Wang, Qingmin,Yue, Fuyang
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supporting information
p. 8924 - 8928
(2021/11/04)
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- Silver-promoted synthesis of vinyl sulfones from vinyl bromides and sulfonyl hydrazides in water
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The synthesis of vinyl sulfones via silver-promoted cross-coupling of vinyl bromides with sulfonyl hydrazides was realized. Water was used as the sole solvent. Multisubstituted vinyl sulfones were easily prepared with excellent alkyl group tolerance. A mechanism involving nucleophilic attack of a sulfinate anion was proposed.
- Zhang, Ge,Fu, Jian-Guo,Zhao, Qian,Zhang, Gui-Shan,Li, Meng-Yao,Feng, Chen-Guo,Lin, Guo-Qiang
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supporting information
p. 4688 - 4691
(2020/05/22)
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- Visible-light induced cascade radical cyclization of sulfinic acids and o-(allyloxy)arylaldehydes towards functionalized chroman-4-ones
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An efficient method for the synthesis of functionalized chroman-4-ones induced by visible light via the radical cyclization reaction of sulfinic acids and o-(allyloxy)arylaldehydes at room temperature was described. The corresponding products were isolate
- Li, Guang-Hui,Han, Qing-Qing,Sun, Yuan-Yuan,Chen, De-Mao,Wang, Zu-Li,Xu, Xin-Ming,Yu, Xian-Yong
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supporting information
p. 3255 - 3258
(2020/03/13)
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- Practical and efficient synthesis of aryl trifluoromethyl sulfones from arylsulfonyl chlorides with Umemoto's reagent II
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A practical and efficient method for the synthesis of aryl trifluoromethyl sulfones has been developed by a tandem reaction of arylsulfonyl chlorides with Umemoto's reagent II. The advantageous features of this method are simple operation, mild reaction conditions, wide scope of substrates, high yield of products, and easy scalability.
- Zhou, Xiaocong,Hu, Dufen,He, Xinyi,Li, Yuanqiang,Chu, Youqun,She, Yuanbin
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supporting information
(2019/12/24)
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- Silver-catalyzed cascade radical cyclization of sodium sulfinates and o-(allyloxy)arylaldehydes towards functionalized chroman-4-ones
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An efficient method for the synthesis of functionalized Chroman-4-ones via cascade radical cyclization of sodium sulfinates and o-(allyloxy)arylaldehydes using silver as catalyst and K2S2O8 as oxidant was presented. The de
- Chen, De-Mao,Han, Qing-Qing,Li, Guang-Hui,Sun, Yuan-Yuan,Wang, Zu-Li,Xu, Xin-Ming,Yu, Xian-Yong
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supporting information
(2020/02/13)
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- Visible-light-mediated difunctionalization of vinylcyclopropanes for the synthesis of 1-sulfonylmethyl-3,4-dihydronaphthalenes
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An efficient method for visible-light-mediated sulfonylation/arylation of the C-C σ-bond in vinylcyclopropanes with sulfonyl chlorides to synthesize 1-sulfonylmethyl-substituted 3,4-dihydronaphalenes has been developed. A radical-type pathway has been proved in this transformation. This difunctionalization procedure shows a series of advantages, such as the use of commercially and easily available sulfonyl chlorides, mild conditions, and eco-friendly energy.
- Wang, Qiao-Lin,Zhang, Wen-Zheng,Zhou, Quan,Zhou, Cong-Shan,Xiong, Bi-Quan,Tang, Ke-Wen,Liu, Yu
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supporting information
p. 7918 - 7926
(2019/09/06)
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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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- Direct C(sp2)-H Arylsulfonylation of Enamides via Iridium(III)-Catalyzed Insertion of Sulfur Dioxide with Aryldiazonium Tetrafluoroborates
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An iridium(III)-catalyzed three-component reaction of enamides, aryldiazonium tetrafluoroborates, and 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO) for the direct C(sp2)?H arylsulfonylation of enamides is developed. This transformation provides a robust and straightforward approach for preparing a diverse array of β-amidovinyl sulfones in moderate to excellent yields and high stereoselectivities without Light-emitting diode (LED) radiation. This transformation also features mild conditions, broad substrate scopes, and excellent functional group tolerance. (Figure presented.).
- Zhu, Tong-Hao,Zhang, Xiao-Chen,Cui, Xian-Lu,Zhang, Ze-Yu,Jiang, Hui,Sun, Shan-Shan,Zhao, Li-Li,Zhao, Kai,Loh, Teck-Peng
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p. 3593 - 3598
(2019/05/27)
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- Manganese(iii) acetate-mediated direct C(sp2)-H-sulfonylation of enamides with sodium and lithium sulfinates
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A Mn(OAc)3 mediated oxidative C(sp2)-H sulfonylation of enamides and encarbamates with sodium and lithium sulfinates is reported. This operationally simple transformation provides a straightforward and highly stereoselective access to (E)-β-amidovinyl sulfones in moderate to excellent yields. The reaction proceeds readily under mild conditions at room temperature and tolerates various sensitive functional groups. This process affords exclusively (E)-configurated β-amidovinyl sulfones independent of the starting material configuration. Moreover, a direct transformation of organolithium reagents and sulfur dioxide into β-amidovinyl sulfones is described.
- Kramer, Philipp,Krieg, Sara-Cathrin,Kelm, Harald,Manolikakes, Georg
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supporting information
p. 5538 - 5544
(2019/06/14)
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- Copper-Catalyzed Amide Radical-Directed Cyanation of Unactivated Csp3-H Bonds
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A method for site-selective intermolecular δ/?-Csp3-H cyanation of aliphatic sulfonamides is developed using TsCN as the cyanating reagent, catalyzed by a Cu(I)/phenanthroline complex. The mild, expeditious, and modular protocol allows efficient remote Csp3-H cyanation with good functional group tolerance and high regioselectivity. Mechanistic studies indicate that the reaction might proceed through a Cu(I)-mediated N-F bond cleavage to generate an amidyl radical, 1,5-HAT, and cyano group transfer of the resulting carbon radical with TsCN.
- Zhang, Hongwei,Zhou, Yulu,Tian, Peiyuan,Jiang, Cuiyu
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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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- Dehydroxymethylation of alcohols enabled by cerium photocatalysis
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Dehydroxymethylation, the direct conversion of alcohol feedstocks as alkyl synthons containing one less carbon atom, is an unconventional and underexplored strategy to exploit the ubiquity and robustness of alcohol materials. Under mild and redox-neutral reaction conditions, utilizing inexpensive cerium catalyst, the photocatalytic dehydroxymethylation platform has been furnished. Enabled by ligand-to-metal charge transfer catalysis, an alcohol functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional alkyl nucleophiles for radical-mediated 1,4-conjugate additions with Michael acceptors. A broad range of alcohols, from simple ethanol to complex nucleosides and steroids, have been successfully applied to this fragment coupling transformation. Furthermore, the modularity of this catalytic system has been demonstrated in diversified radical-mediated transformations including hydrogenation, amination, alkenylation, and oxidation.
- Zhang, Kaining,Chang, Liang,An, Qing,Wang, Xin,Zuo, Zhiwei
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supporting information
p. 10556 - 10564
(2019/08/20)
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- Dehydroxymethylation of Alcohols Enabled by Cerium Photocatalysis
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Dehydroxymethylation, the direct conversion of alcohol feedstocks as alkyl synthons containing one less carbon atom, is an unconventional and underexplored strategy to exploit the ubiquity and robustness of alcohol materials. Under mild and redox-neutral reaction conditions, utilizing inexpensive cerium catalyst, the photocatalytic dehydroxymethylation platform has been furnished. Enabled by ligand-to-metal charge transfer catalysis, an alcohol functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional alkyl nucleophiles for radical-mediated 1,4-conjugate additions with Michael acceptors. A broad range of alcohols, from simple ethanol to complex nucleosides and steroids, have been successfully applied to this fragment coupling transformation. Furthermore, the modularity of this catalytic system has been demonstrated in diversified radical-mediated transformations including hydrogenation, amination, alkenylation, and oxidation.
- Zhang, Kaining,Chang, Liang,An, Qing,Wang, Xin,Zuo, Zhiwei
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supporting information
p. 10556 - 10564
(2019/08/28)
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- Synthesis of aromatic sulfonamides through a copper-catalyzed coupling of aryldiazonium tetrafluoroborates, DABCO·(SO2)2, and N-Chloroamines
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A copper-catalyzed aminosulfonylation of aryldiazonium tetrafluoroborates, DABCO·(SO2)2, and N-chloroamines is described. This coupling reaction provides an efficient and simple approach to a wide range of sulfonamides in moderate to good yields under mild conditions. Mechanistic investigation suggests that a radical process and transition-metal catalysis are merged in this tandem reaction.
- Zhang, Feng,Zheng, Danqing,Lai, Lifang,Cheng, Jiang,Sun, Jiangtao,Wu, Jie
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p. 1167 - 1170
(2018/02/23)
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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 Difluoromethylthioesters from Aldehydes
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Difluoromethylthioester compounds are yet another important kind of organofluorine compound and are reported here for the first time. They can be efficiently synthesized from various aldehydes. The synthetic method features mild reaction conditions, good
- Guo, Shi-Huan,Zhang, Xing-Long,Pan, Gao-Fei,Zhu, Xue-Qing,Gao, Ya-Ru,Wang, Yong-Qiang
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supporting information
p. 1663 - 1667
(2018/01/27)
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- Iodine-Mediated Difunctionalization of Imidazopyridines with Sodium Sulfinates: Synthesis of Sulfones and Sulfides
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Novel iodine-induced sulfonylation and sulfenylation of imidazopyridines have been described using sodium sulfinates as the sulfur source. This strategy enables highly selective difunctionalization of imidazo[1,2-a]pyridine to access sulfones and sulfides in good yields. A wide range of substrates and functional groups were well-tolerated under optimized conditions. Moreover, control experiments have been conducted, indicating a radical pathway involved in the reaction mechanisms.
- Guo, Yu-Jing,Lu, Shuai,Tian, Lu-Lu,Huang, En-Ling,Hao, Xin-Qi,Zhu, Xinju,Shao, Tian,Song, Mao-Ping
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p. 338 - 349
(2018/02/19)
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- Dual gold and photoredox catalysis: visible light-mediated intermolecular atom transfer thiosulfonylation of alkenes
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Regioselective difunctionalization of alkenes has attracted significant attention from synthetic chemists and has the advantage of introducing diverse functional groups into vicinal carbons of common alkene moieties in a single operation. Herein, we report an unprecedented intermolecular atom transfer thiosulfonylation reaction of alkenes by combining gold catalysis and visible-light photoredox catalysis. A trifluoromethylthio group (SCF3) and other functionalized thio groups together with a sulfonyl group were regioselectively introduced into alkenes in the most atom economical manner. A detailed mechanism study indicated that a synergistic combination of gold catalysis and photoredox catalysis is crucial for this reaction.
- Li, Haoyu,Shan, Cuicui,Tung, Chen-Ho,Xu, Zhenghu
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p. 2610 - 2615
(2017/04/06)
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- A Route to O-Aminosulfonates and Sulfonamides through Insertion of Sulfur Dioxide and Hydrogen Atom Transfer
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A three-component reaction of aryldiazonium tetrafluoroborates, the 1,4-diazabicyclo[2.2.2]octane?bis(sulfur dioxide) adduct [DABCO?(SO2)2] and hydroxylamines under catalyst-free and additive-free conditions has been developed, providing aryl O-aminosulfonates in good yields. Sulfonamides could also be obtained via a one-pot process through the reaction of aryldiazonium tetrafluoroborates, DABCO?(SO2)2 and amines in the presence of N-hydroxybenzotriazole. A mechanism involving the insertion of sulfur dioxide and hydrogen atom transfer is proposed and supported by theoretical calculations. (Figure presented.).
- Liu, Tong,Zheng, Danqing,Li, Zhenhua,Wu, Jie
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p. 2653 - 2659
(2017/08/16)
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- Nickel-Catalyzed Sulfonylation of C(sp2)–H Bonds with Sodium Sulfinates
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The first nickel-catalyzed ortho-sulfonylation of C(sp2)–H bonds with sodium sulfinates directed by (pyridin-2-yl)isopropylamine (PIP-amine) is described. This strategy exhibits a broad substrate scope and good functional group tolerance with high monosulfonylation selectivity. Besides arenes and heteroarenes, the reaction can also be extended to alkenes, providing diverse diaryl and alkyl aryl sulfones in high yields. Furthermore, a plausible Ni(I)/Ni(III) mechanism is outlined based on our experimental results and related precedents. (Figure presented.).
- Liu, Shuang-Liang,Li, Xue-Hong,Zhang, Shu-Sheng,Hou, Sheng-Kai,Yang, Guang-Chao,Gong, Jun-Fang,Song, Mao-Ping
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supporting information
p. 2241 - 2246
(2017/07/07)
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- Photoredox α-vinylation of α-amino acids and N -aryl amines
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A new coupling protocol has been developed that allows the union of vinyl sulfones with photoredox-generated α-amino radicals to provide allylic amines of broad diversity. Direct C-H vinylations of N-aryl tertiary amines, as well as decarboxylative vinylations of N-Boc α-amino acids, proceed in high yield and with excellent olefin geometry control. The utility of this new allyl amine forming reaction has been demonstrated via the syntheses of several natural products and a number of established pharmacophores.
- Noble, Adam,MacMillan, David W. C.
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supporting information
p. 11602 - 11605
(2014/11/08)
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- Palladium-catalyzed cascade reaction of α,β-unsaturated sulfones with aryl iodides
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Unlike traditionally used acyclic 1,2-disubstituted alkenes, the reaction of α,β-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions (Pd(OAc)2 as catalyst, Ag2-CO3 as base in DMF at 120°C) takes place mainly by a cascade process, involving one unit of the alkene and three units of the aryl iodide, to afford a substituted 9-phenylsulfonyl-9,10-dihydrophenanthrene, The dominant formation of this 3:1 coupling product, instead of the Heck trisubstituted olefin, shows that aromatic C-H activation processes can compete with the usually fast syn β-hydrogen elimination step in the Heck arylation of an acyclic olefin. The structural scope of this palladium-catalyzed cascade arylation of α,β-unsaturated sulfones has proved to be wide with regard to substitution at the β-position (alkyl, aryl, or alkenyl substitution), substitution at the sulfone unit (alkyl or phenyl sulfones), and configuration at the C=C bond (trans or cis). Moreover, although less favored than in the case of the arylation of α,β-unsaturated sulfones, similarly substituted 9,10-dihydrophenanthrenes have also been obtained in the case of α,β-unsaturated phosphine oxides and α,β-unsaturated phosphonate esters. A Pd0-pdII-pdIV mechanistic pathway involving the successive formation of highly electrophilic σ-alkylpalladium intermediates and palladacycles is proposed for this multi-component arylation.
- Mauleon, Pablo,Nunez, Angel A.,Alonso, Ines,Carretero, Juan C.
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p. 1511 - 1520
(2007/10/03)
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- Unusual palladium-catalyzed cascade arylation of α,β-unsaturated phenyl sulfones under heck reaction conditions
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Four C-C bonds are formed in a single step by an intermolecular four-component cascade pathway. 1-Phenyl-9-phenylsulfonyl-9,10-dihydrophenanthrenes are formed in the palladium-catalyzed Heck-like reaction of α,β-unsaturated phenyl sulfones with three equivalents of iodobenzene in the presence of Ag2CO3 [Eq. (1)].
- Mauleoandn, Pablo,Alonso, Ineands,Carretero, Juan C.
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p. 1291 - 1293
(2007/10/03)
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- On the Reaction of 1,1-Diphenylethene with Arenediazonium Chlorides and SO2
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1,1-diphenylethene reacts with arenediazonium chlorides and SO2 in the presence of CuCl2 in solution of water-acetone-acetic acid (1 : 1 : 1) mainly to form products of substitution of hydrogen atom by arylsulphonyl group, aryl(2,2-
- Bilaya,Obushak,Ganushchak,Buchinskii
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p. 1477 - 1479
(2007/10/03)
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- Reagents for rapid peptide synthesis
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This invention relates to compounds of the formula: STR1 wherein R is an electron withdrawing group; R1 is H or COZ; X1 and X2 are independently H, lower alkyl, aryl, aryl lower-alkyl or polystyrene or R and X1 taken together with the carbon atoms to which they are attached form a ring containing from 4 to 15 ring carbon atoms and may contain up to 2 heteroatoms, wherein the heteroatoms are O, S, or N; and Z is an amino acid residue, a peptide residue or a leaving group. The compounds of the present invention are adaptable as blocking or protecting groups for an amine composition useful in peptide synthesis. The present invention is also directed to a method of protecting an amino group of an organic molecule during a reaction which modifies a portion of the molecule other than the protected amino group.
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- A New Version of the Peterson Olefination Using Bis(trimethylsilyl)methyl Derivatives and Fluoride Ion as Catalyst
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Reaction between a variety of bis(trimethylsilyl)methyl derivatives and carbonyl compounds under fluoride ion as catalyst is described.The reaction works especially well with nonenolizable carbonyl compounds to give the expected alkenes in high yields and, in some cases, with high stereoselectivity.Application of this methodology to an intramolecular alkenation providing a tricyclic benzocarbacephem ring system is also described.
- Palomo, Claudio,Aizpurua, Jesus M.,Garcia, Jesus M.,Ganboa, Inaki,Cossio, F. P.,et al.
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p. 2498 - 2503
(2007/10/02)
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- Reactions of Alkylmercurials with Heteroatom-Centered Acceptor Radicals
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The relative reactivities of alkylmercury halides toward PhS., PhSe., or I. decrease drastically from R = tert-butyl to R = sec-alkyl to R = n-butyl, indicative that R. is formed in the rate-determining step in the attack of these radicals upon RHgCl.The alkyl radicals thus formed will enter into chain reactions in which a heteroatom-centered radical (A.) is regenerated from substrates such as RS-SR, ArSe-SeAr, ArTe-TeAr, PhSe-SO2Ar, Cl-SO2Ph; ZCH=CHA (A = Cl, I, SPh, SO2Ph); or PhCCHA (A = I, SPh, SO2Ph). β-Styrenyl (PhCH=CHA, Ph2C=CHA) and β-phenethynyl (PhCCA) systems with A = I, Br, SO2Ph also enter into chain reactions with mercury(II) salts with the ligands PhS, PhSe, PhSO2, or (EtO)2PO.The relative reactivities of a series of reagents toward t-Bu. and of PhCH=CHA, Ph2C=CHA, and PhCCA toward c-C6H11. are reported as well as the regioselectivity of t-Bu. attack observed for 1,2-disubstituted ethylenes (ZCH=CHA) with Z and A from the group Ph, Cl, Br, I, SO2Ph, SPh, Bu3Sn.Reactions of (E)- and (Z)-PhCH=CHI or MeO2CCH=CHI with t-Bu. or c-C6H11. occurred in a regioselective and stereospecific (retention) manner.Reactions of (E)- and (Z)-ClCH=CHCl occurred in a nonstereospecific manner in which the E/Z product ratio increased with the bulk of the attacking radical.A similar effect on the E/Z product ratios was observed for (Z)-MeO2CCH=CHCl.
- Russell, Glen A.,Ngoviwatchai, Preecha,Tashtoush, Hasan I.,Pla-Dalmau, Anna,Khanna, Rajive K.
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p. 3530 - 3538
(2007/10/02)
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- Synthesis of Alkenes via Peterson Reaction
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The α-phenylthiosilanes (2) have been used to prepare the α-silyl anions (1) by reaction with lithium naphthalenide; subsequent condensation with a carbonyl compound gave the alkene (8) via the Peterson reaction.The α-phenylthiosilanes (2) were prepared from n,n-bis(phenylthio)acetals (4) by reaction with lithium naphthalenide and chlorotrimethylsilane.The n,n-bis(phenylthio)acetals (4) were obtained, in turn, from 1,1-bis(phenylthio)acetals (5) by anion formation with butyl-lithium-N,N,N',N'-tetramethylethylenediamine complex in hexane followed by reaction with an alkyl halide.The Peterson reaction was also used to prepare vinyl sulphides (9) and vinyl sulphones (13).
- Ager, David J.
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p. 183 - 194
(2007/10/02)
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- Sulfone reagents in organic synthesis. VI. Sulfonyl- and silyl-substituted hydrocarbons as versatile carbanion precursors in organic synthesis
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The basic organometallic chemistry of β-silyl-substituted acetylenic, vinylic and alkyl sulfones has been investigated, with attention being given to metallation, carbometallation and the chemical reduction of carbon-carbon unsaturation. 2-Trimethylsilylvinyl and 2-trimethylsilylalkyl sulfones underwent smooth and stereoselective lithiation with RLi on the carbon α to the sulfonyl group. Carbometallation of vinyl sulfones could be achieved with RMgX or LiCuR2, but acetylenic sulfones carbometallated smoothly only with LiCuR2; with RMgX or RLi, these acetylenes underwent alkyldesulfonylation. The utility in synthesis of these metallo derivatives of sulfonyl-silyl-hydrocarbons is discussed and their value in elaborating carbon skeletons is illustrated for the preparation of alkenes, allenes, carbocycles and stereo-defined vinyl sulfones.
- Eisch, John J.,Behrooz, Mohammad,Dua, Suresh K.
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p. 121 - 136
(2007/10/02)
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- ELECTRON-TRANSFER PROCESSES IN THE ALKYLATION OF α,β-UNSATURATED SULFONES BY ORGANOMETALLIC REAGENTS
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The alkyldesulfonylation of acetylenic and vinylic sulfones by organolithium and organomagnesium reagents is shown to take place via alkyl radicals arising from electrontransfer processes.
- Eisch, John J.,Behrooz, Mohammad,Galle, James E.
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p. 4851 - 4854
(2007/10/02)
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- Reactions of α-Silylsulphones
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α-Silylsulphones have been utilised to prepare vinylsulphones via the Peterson reaction and ketones by alkylation, reduction, and sila-Pummerer rearrangement.
- Ager, David J.
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p. 486 - 488
(2007/10/02)
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- Reactions of Arenesulfonyl Chlorides with Olefins Catalyzed by a Ruthenium(II) Complex
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Arenesulfonyl chlorides react with vinylarenes in the presence of dichlorotris(triphenylphosphine)ruthenium(II) catalyst and 1 molar equiv of a tertiary amine to form α,β-unsaturated sulfones 2.Only the E isomers of the sulfones are formed.In reactions of arenesulfonyl chlorides containing an electron-withdrawing Cl or NO2 substituent with α-methylstyrenes, 2-aryl-3-(arylsulfonyl)propenes (5) are also formed.Mechanisms for these reactions are proposed.
- Kamigata, Nobumasa,Sawada, Hideo,Kobayashi, Michio
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p. 3793 - 3796
(2007/10/02)
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