- SIMPLE AND CONVENIENT METHOD FOR THE SYNTHESIS OF SULFONES USING POLYETHYLENE GLYCOLS OR THEIR DIALKYL ETHERS AS SOLVENTS OR CATALYSTS.
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Various alkyl p-tolyl sulfones were prepared in good yields under mild conditions in the presence of polyethyene glycols or their dialkyl ethers as solvents or catalysts.
- Sukata
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Read Online
- The free-radical cyclization reaction of 1,6-dienes with selenosulfonate
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A sulfonyl radical induced addition-cyclization reaction of 1,6-dienes with p-tolyl benzeneselenosulfonate giving functionalized cyclopentane system is described.
- Chuang
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Read Online
- Isomerisation of Vinyl Sulfones for the Stereoselective Synthesis of Vinyl Azides
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Reported is the construction, and facile base-mediated conversation of ten differently substituted 3-azido E-vinyl sulfones (γ-azido-α,β-unsaturated sulfones) into their isomeric vinyl azide counterparts. The requisite 3-azido E-vinyl sulfones were prepared from 3-bromo E-vinyl sulfones, which in turn were accessed from allyl sulfones via a bromination-elimination sequence. In relation to this a one-pot azidation-isomerisation sequence was developed which enabled the direct formation of the vinyl azides from the corresponding 3-bromo E-vinyl sulfones. Similarly, a convenient one-pot Horner–Wadsworth–Emmons olefination-isomerisation approach was utilised in order to prepare some of the allylic sulfones used in this study. The vinyl azide forming process typically proceeded with high levels of Z-selectivity, although this was dependent on the vinyl sulfone substitution pattern. Thus, with either no substituent or a methyl group in the γ- or β-position, relative to the sulfone, good, to high levels of Z-selectivity (Z/E = 85:15 to ≥ 95:5) were obtained. However, incorporation of an α-sulfonyl methyl substituent led to an E-selective process (Z/E = 20:80). A non-bonding interaction between the azido group and the α-sulfonyl vinylic proton is proposed, which acts as a conformational control mechanism to help guide the stereochemical outcome.
- Collins, Niall,Connon, Robert,Evans, Paul,Sánchez-Sanz, Goar
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supporting information
p. 6228 - 6235
(2020/10/02)
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- Water-Promoted Dehydrative Tsuji–Trost Reaction of Non-Derivatized Allylic Alcohols with Sulfinic Acids
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A mild, green and extra activator-free synthesis of allylic sulfones from non-derivatized allylic alcohols and sulfinic acids was developed and only the easily-available Pd(PPh3)4 was used as the catalyst. This new method could be easily scaled up to gram scale, affording the target allylic sulfones in a nearly quantitative yield with water as the sole by-product. Mechanism studies both by various NMR techniques and by theoretical calculations suggested two reaction pathways may be involved in the reaction, which are dependent on the reaction media, that is, an eight-membered ring binding species may be formed in aqueous media between allylic alcohol, sulfinic acid and water, while a six-membered ring binding species may be formed in common aprotic organic solvent between allylic alcohol and sulfinic acid. Both binding species may be accounted for the efficient activation of allylic alcohols via hydrogen bonding.
- Yu, Jing,Chang, Xueping,Ma, Ruitian,Zhou, Qiuju,Wei, Mengmeng,Cao, Xinhua,Ma, Xiantao
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supporting information
p. 7238 - 7242
(2020/10/30)
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- A General Photocatalytic Route to Prenylation
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Prenylation is an essential reaction on which nature relies to modify properties of molecules and build terpenoids, but remains a challenging chemical reaction. Aiming to capitalize on recent advances in photocatalysis to easily and cleanly generate a broad range of carbon based radicals, we have developed a prenyl transfer reagent that is captured by transiently generated radicals. The reagent can be made in bulk, is bench stable, and broadly applicable such that it can be used with existing photocatalytic methods with very few changes to reaction conditions. Ultimately, this provides a true drop-in solution for prenylation, expanding the scope of substrates that can be readily prenylated.
- Rathnayake, Manjula D.,Weaver, Jimmie D.
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supporting information
p. 1433 - 1438
(2019/06/13)
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- A practical synthesis of functionalized isoindolinones via [3?+?3] benzannulation of 1,3-bissulfonylpropenes and 4-arylmethylene-2,3-dioxopyrrolidines
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A straightforward synthesis of isoindolinones has been developed via a [3 + 3] benzannulation of 4-arylmethylene-2,3-dioxopyrrolidines and 1,3-bissulfonylpropenes (or 4-sulfonylcrotonates). A series of functionalized isoindolinones were obtained in excellent yields. The reaction could be carried out under mild conditions without transition metal catalyst. The finding provides a practical approach for the preparation of isoindolinone derivatives with potential biological activities.
- Tang, Xiang-zheng,zhou, Jing-xuan,Liang, Hua-ju,Zhang, Xue-jing,Yan, Ming,Chan, Albert S.C.
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supporting information
p. 147 - 149
(2018/12/11)
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- One-Pot Allylation-Intramolecular Vinylogous Michael Addition-Isomerization Cascade of o-Hydroxycinnamates and Congeners: Synthesis of Substituted Benzofuran Derivatives
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A unique intramolecular vinylogous Michael addition leading to the synthesis of heterocycles has been disclosed. Base-promoted one-pot sequential O-allylation of o-hydroxy-cinnamates or -cinnamonitrile or -chalcones with γ-bromocrotonates followed by an intramolecular conjugate addition of vinylogous Michael donors resulted in the formation of highly substituted benzofuran derivatives in good to excellent yields. The intramolecular event followed by two [1,3]-H shifts leading to aromatization appears to be the key to the success of this unprecedented transformation.
- Harish, Battu,Subbireddy, Manyam,Obulesu, Owk,Suresh, Surisetti
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supporting information
(2019/03/19)
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- Oxidation of sulfides including DBT using a new vanadyl complex of a non-innocent o-aminophenol benzoxazole based ligand
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Reaction of a non-innocent o-aminophenol benzoxazole based ligand HLBAP with VOCl3 afforded a vanadyl complex, VOLBIS (SQ), in which SQ is a 2,4-di-tert-butylsemiquinone produced from hydrolysis of HLBAP. The crystal structure of VOLBIS (SQ) exhibits an octahedral geometry with the VO2+ center coordinated by two nitrogen and one oxygen atoms of LBAP and two oxygen atoms of SQ. Electrochemical studies showed quasi-reversible metal-centered reduction and ligand-centered oxidation of complex. The magnetic moment of VOLBIS (SQ) is consistent with the spin-only value expected for S?=?1/2 system. The neutral species of VOLBIS (SQ) is EPR active, which is consistent with a paramagnetic electronic ground state (S?=?1/2). This result is in accordance with the vanadyl (IV) moiety surrounded by tridentate iminobenzosemiquinonate anion radical (HLBIS)?- and benzosemiquinone ligand (SQ)?. The theoretical calculations confirm the experimental results. Furthermore, we present the optimal conditions for maximum efficiency of sulfide oxidation for oxidative desulfurization with hydrogen peroxide and 6 times reusability of catalyst for sulfoxidation of dibenzothiophene.
- Saeedi, Roonak,Safaei, Elham,Lee, Yong-Ill,Lu?nik, Janez
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- SO2 conversion to sulfones: Development and mechanistic insights of a sulfonylative Hiyama cross-coupling
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A Pd-catalyzed Hiyama cross-coupling reaction using SO2 is described. The use of silicon-based nucleophiles leads to the formation of allyl sulfones under mild conditions with a broad functional group tolerance. Control experiments coupled with DFT calculations shed light on the key steps of the reaction mechanism, revealing the crucial role of a transient sulfinate anion.
- Adenot, Aurélien,Char, Jo?lle,Von Wolff, Niklas,Lefèvre, Guillaume,Anthore-Dalion, Lucile,Cantat, Thibault
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supporting information
p. 12924 - 12927
(2019/11/05)
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- Facile synthesis of substituted diaryl sulfones: Via a [3 + 3] benzannulation strategy
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A base-mediated [3 + 3] benzannulation strategy for the conversion of 1,3-bis(sulfonyl)propenes and β,γ-unsaturated α-ketoesters to diaryl sulfones has been developed. This method provides facile, metal-free and efficient access to highly substituted diaryl sulfones in good to excellent yields. In addition, the sulfonyl group could be easily removed or converted to other functional groups via an organostannane intermediate.
- Tang, Xiang-Zheng,Tong, Lang,Liang, Hua-Ju,Liang, Jie,Zou, Yong,Zhang, Xue-Jing,Yan, Ming,Chan, Albert S. C.
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supporting information
p. 3560 - 3563
(2018/05/26)
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- Oxygenation of sulfides catalysed by SBA-15-immobilized molybdenum(VI) complex of a bis(phenol) diamine ligand using aqueous hydrogen peroxide as a green oxidant
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A highly efficient and reusable molybdenum-based catalyst has been synthesized by covalent grafting of a bis(phenol) diamine ligand, namely 2-(((2-bromoethyl)(2-((3,5-di-tert-butyl-2-hydroxybenzyl)amino)ethyl)amino)methyl)-4,6-di-tert-butylphenol, onto functionalized ordered mesoporous silica (SBA-15) followed by complexation with MoO2(acac)2. The resulting organic–inorganic hybrid material was found to be a highly effective catalyst for oxygenation of various sulfides to their corresponding sulfoxides or sulfones. The catalyst was characterized using transmission and scanning electron microscopies, X-ray photoelectron, Fourier transform infrared and atomic absorption spectroscopies, Brunauer–Emmett–Teller surface area analysis and thermogravimetric analysis. Mild reaction conditions, high selectivity and easy recovery and reusability of the catalyst render the presented protocol very useful for addressing industrial needs and environmental concerns.
- Saberikia, Iraj,Safaei, Elham,Karimi, Babak,Lee, Yong-Iii
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- Direct N-H/α,α,β,β-C(sp3)-H functionalization of piperidine via an azomethine ylide route: synthesis of spirooxindoles bearing 3-substituted oxindoles
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A protocol for the direct functionalization of N-H/α,α,β,β-C(sp3)-H of piperidine without any metal or external oxidants is reported. This reaction is promoted by 4-(trifluoromethyl)benzoic acid via an azomethine ylide intermediate. This is a simple method for the synthesis of spirooxindoles bearing 3-substituted oxindole moieties.
- Du, Yanlong,Yu, Aimin,Jia, Jiru,Zhang, Youquan,Meng, Xiangtai
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supporting information
p. 1684 - 1687
(2017/02/10)
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- Process for the Synthesis of Sulfones and Sulfonamides
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A one pot single step process is described for the synthesis of a compound, including a labeled compound, containing a sulfonyl functional group comprising the step of mixing together a silane, an SO2 source, an electrophilic compound, an activ
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Paragraph 0268; 0269; 0270; 0271; 0272
(2017/07/06)
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- Efficient synthesis of aliphatic sulfones by Mg mediated coupling reactions of sulfonyl chlorides and aliphatic halides
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Sulfonyl chlorides were reduced to anhydrous sulfinate salts with magnesium under sonication. These sulfinates were alkylated to sulfones with alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic sulfones was efficiently prepared by this one-pot two-step procedure.
- Fu, Ying,Xu, Qin-Shan,Li, Quan-Zhou,Du, Zhengyin,Wang, Ke-Hu,Huang, Danfeng,Hu, Yulai
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p. 2841 - 2845
(2017/04/03)
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- One-pot synthesis of substituted tetrahydrocyclobuta[a]naphthalenes by domino aldol condensation/olefin migration/electrocyclization
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A facile one-pot synthetic route for preparing the novel benzofused tricyclic skeleton of 1,2,2a,8b-tetrahydrocyclobuta[a]naphthalenes 5 is developed. The route was realized by a NaH-mediated tandem aldol condensation/olefin migration/electrocyclization of o-allylbenzaldehydes 1 with cinnamyl sulfones 3 in good yields.
- Chang, Meng-Yang,Wu, Ming-Hao,Chen, Yeh-Long
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supporting information
p. 2822 - 2825
(2013/07/26)
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- Aerobic palladium-catalyzed arylation of alkenes using sodium sulfinates
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Palladium-catalyzed oxidative arylations of terminal alkenes could be performed using sodium sulfinates at 60 °C in air. The procedure gave various aryl alkenes after the desulfonylation of sodium arylsulfinates in the presence of a palladium catalyst. For instance, the reaction of styrene with sodium phenylsulfinate afforded trans-1,2-diphenylethylene in 80% yield without the formation of other stereoisomers. Georg Thieme Verlag Stuttgart · New York.
- Taniguchi, Nobukazu
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supporting information
p. 2571 - 2574
(2013/12/04)
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- Coupling reaction of magnesium alkylidene carbenoids with α-sulfonylallyllithiums: An efficient route to multi-substituted vinylallenes
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A variety of vinylallenes were successfully synthesized from 1-chlorovinyl p-tolyl sulfoxides and allyl or vinyl sulfones. Allyl and vinyl sulfones served as α-sulfonylallyllithium sources were prepared from carbonyl compounds in three or four steps in good overall yields. The coupling reaction of α-sulfonylallyllithiums with magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides and isopropylmagnesium chloride, afforded multi-substituted vinylallenes in up to 88% yield. Georg Thieme Verlag KG Stuttgart · New York.
- Kimura, Tsutomu,Kobayashi, Gen,Ishigaki, Masashi,Inumaru, Mio,Sakurada, Jo,Satoh, Tsuyoshi
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p. 3623 - 3632
(2013/02/23)
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- Preliminary investigations on novel camphor-derived chiral sulfones: Completely stereoselective formation of tricyclic β-hydroxy sulfones from 8- and 10-functionalized camphor derivatives
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Some camphor-derived chiral allylic and benzylic sulfones in which the sulfonyl group is located at the C-10, C-9 or C-8 methyl groups of (+)-camphor were synthesized. The C-9 and C-8 substituted sulfones were obtained via Wagner-Meerwein rearrangements of the bicyclic camphor framework. On treatment with LDA, the C-10 and C-8 substituted sulfones cyclized with complete stereoselectivity, affording tricyclic β-hydroxy sulfones whose relative configurations were determined by X-ray crystallography. Tricyclic sulfones 23 and 24 underwent both β-elimination and retro-aldol reactions on further exposure to base. Reduction of the carbonyl group of the C-10 substituted sulfones afforded exo-configured isobornyl sulfones with high stereoselectivity. Reaction of the lithiated isobornyl benzyl sulfone 32 with benzaldehyde generated all four of the possible product diastereomers, of which three were isolated pure by chromatography. Attempted desulfonylation of these diastereomers failed to generate the desired optically active homobenzylic alcohols but the same sulfonyl carbanion trapping/desulfonylation sequence was successful in a model achiral series of compounds.
- Lewis, Frank W.,McCabe, Thomas C.,Grayson, David H.
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supporting information; experimental part
p. 7517 - 7528
(2011/10/12)
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- Vanadium-catalyzed enantioselective oxidation of allyl sulfides
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The enantioselective oxidation of allyl sulfides with a vanadyl complex of 3,5-diiodosalicylidene tert-leucinol as a catalyst and aqueous hydrogen peroxide as an oxidant afforded chiral allyl sulfoxides with high enantioselectivities of up to 97.3% ee and moderate yields.
- Zeng, Qingle,Gao, Yuxing,Dong, Junyu,Weng, Wen,Zhao, Yufen
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p. 717 - 721
(2011/08/06)
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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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supporting information; experimental part
p. 1308 - 1312
(2011/07/07)
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- Novel synthesis of pinacols and sulfones promoted by Smi£ NiCl2 bimetallic system
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Smi£NiCl2 as a reductive system promoted reductive coupling of aryl adehydes and aryl ketone into pinacols in good yields and also promoted coupling reaction of aryl sulfonyl chlorides and active halides into sulfones in good yields.
- Ye, Yuyuan,Zhou, Qizhong,Zheng, Renhua,Jiang, Huajiang,Chen, Rener,Zhang, Yongmin
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experimental part
p. 331 - 334
(2012/05/04)
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- Linear-selective rhodium(I)-catalyzed addition of arylboronic acids to allyl sulfones
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One step further: The rhodium(I)-catalyzed addition of readily available arylboronic acids to allyl sulfones affords the linear (formal) hydroarylated products in good yields and excellent regioselectivities. The reaction broadens the scope of unactivated
- Tsui, Gavin C.,Lautens, Mark
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supporting information; experimental part
p. 8938 - 8941
(2011/02/21)
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- Hydride affinities of cumulated, isolated, and conjugated dienes in acetonitrile
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(Chemical Equation Presented) The hydride affinities (defined as the enthalpy changes in this work) of 15 polarized dienes [five phenyl sulfone substituted allenes (1a), the corresponding five isolated dienes (1b), and the corresponding five conjugated dienes (1c)] in acetonitrile solution were determined by titration calorimetry for the first time. The results display that the hydride affinity scales of the 15 dienes in acetonitrile range from -71.6 to -73.9 kcal/mol for 1a, from -46.2 to -49.7 kcal/mol for 1b, and from -45.0 to -46.5 kcal/mol for 1c, which indicates that the hydride-obtaining abilities of the cumulated dienes (1a) are not only much larger than those of the corresponding conjugated dienes (1c) but also much larger than those of the corresponding isolated dienes (1b). The hydrogen affinities of the 15 dienes as well as the hydrogen affinities and the proton affinities of the radical anions of the dienes (1-.) in acetonitrile were also evaluated by using relative thermodynamic cycles according to Hess's law. The results show that (i) the hydrogen affinities of the neutral dienes 1 cover a range from -44.5 to -45.6 kcal/mol for 1a, from -20.4 to -21.4 kcal/ mol for 1b, and from -17.3 to -18.5 kcal/mol for 1c; (ii) the hydrogen affinities of the radical anions of the dienes (1-.) in acetonitrile cover a range from -40.6 to -47.2 kcal/mol for 1a-., from -21.6 to -29.6 kcal/mol for 1b-., and from -10.0 to -15.4 kcal/mol for 1c-.; (iii) the proton affinities of the 15 1a-. in acetonitrile cover a range from -97.0 to -100.6 kcal/mol for 1a-., from -77.8 to -83.4 kcal/ mol for 1b -., and from -66.2 to -68.9 kcal/mol for 1c-.. The main reasons for the great difference between the cumulated dienes and the corresponding isolated and conjugated dienes in the hydride affinity, hydrogen affinity, and proton affinity have been examined. It is evident that these experimental results should be quite valuable to facilitate the elucidation of the origins of the especially high chemical potencies of the allenes, the choice of suitable hydride reducing agents to reduce the dienes, and the analyses on the reduction mechanisms.
- Zhu, Xiao-Qing,Liang, Hao,Zhu, Yan,Cheng, Jin-Pei
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experimental part
p. 8403 - 8410
(2009/04/11)
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- Ether aryl sulfonic acid esters with improved antimalarial/anticancer activities
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Our previous report showed that our current benchmark agent, 4-methoxyphenyl p-toluenesulibnate, is a selective antimalarial/anticancer agent. A series of related sulfones and sulfonic acid esters is now examined. 4-Allyloxyphenyl p-toluenesulfonate is a superior antimalarial/anticancer agent. 4-Methoxyphenyl 4-nitrobenzenesulfonate is a superior antimalarial agent, but shows poorer inhibition of human skin cancer cells. CSIRO 2006.
- Betts, Lynn M.,Tam, Nga Chiu,Kabir, S. M. Humayun,Langler, Richard F.,Crandall, Ian
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p. 277 - 282
(2008/02/08)
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- Organic reactions in ionic liquids: An efficient method for the synthesis of aryl sulfones by alkylation of sodium arenesulfinates with alkyl halides
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An ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) is used as a reusable reaction medium for the alkylation of sodium arenesulfinates with alkyl halides. This procedure is convenient, efficient and generally gives rise to the S-alkylated product with high selectivity when applied to active halides.
- Hu, Yi,Chen, Zhen-Chu,Le, Zhang-Gao,Zheng, Qin-Guo
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p. 267 - 269
(2007/10/03)
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- Tin-free radical-mediated C-C-bond formations with alkyl allyl sulfones as radical precursors
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Primary alkyl radicals are generated highly efficiently and reliably from alkyl allyl sulfone precursors. The latter are effective in tin-free radical C-C-bond formations, including cyanation, vinylation, and allylation (see scheme; V-40 = 1,1′-azobis(cyc
- Kim, Sunggak,Lim, Chae Jo
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p. 3265 - 3267
(2007/10/03)
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- Aluminum chloride-iron promoted coupling of sulfonyl chlorides with alkyl halides in aqueous media
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A simple and inexpensive procedure for the coupling of sulfonyl chlorides and alkyl halides with aluminum chloride-iron system at ambient temperature in high yield is achieved in aqueous media.
- Saikia, Promod,Laskar, Dhrubojyoti D.,Prajapati, Dipak,Sandhu, Jagir S.
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p. 512 - 513
(2007/10/03)
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- Synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system
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A simple and convenient procedure for the synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system in tetrahydrofuran is presented.
- Zhang, Jiming,Zhang, Yongmin
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p. 516 - 517
(2007/10/03)
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- Bi or Cd-induced coupling of sulfonyl chlorides with allylic halides. A simple synthesis of allylic sulfones
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The bismuth or cadmium-catalyzed coupling reaction between aryl and alkyl sulfonyl chlorides and allylic halides proceeds smoothly to provide excellent yields of allylic sulfones at ambient temperature.
- Baruah, Mukulesh,Boruah, Anima,Prajapati, Dipak,Sandhu, Jagir S.
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p. 1083 - 1084
(2007/10/03)
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- A convenient synthesis of sulfones using zinc mediated coupling reaction of sulfonyl chlorides with alkyl halides in aqueous media
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An efficient procedure for the preparation of sulfones has been developed through a simple reaction of aromatic sulfonyl chlorides with suitable alkyl halides mediated by commercial zinc powder in aqueous media at 0 °C ~ room temperature.
- Sun, Xinghua,Wang, Lei,Zhang, Yongmin
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p. 1785 - 1791
(2007/10/03)
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- A new synthetic route to sulfones via activated nickel-assisted reactions of arenesulfonyl chlorides with active halides
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Various sulfones were prepared in moderate yields by ultrasonic activated nickel-assisted coupling reactions of arenesulfonyl chlorides with alkyl halides.
- Li, Hongbin,Wang, Hui,Pan, Yi,Shi, Yaozeng
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p. 409 - 415
(2007/10/03)
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- Indium-mediated Coupling Reaction of Sulfonyl Chlorides with Alkyl Bromides in Water. A Facile Synthesis of Sulfones
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Indium-mediated coupling of alkyl bromides with aromatic sulfonyl chlorides gives the corresponding sulfones in aqueous media with moderate to good yields.
- Wang, Lei,Zhang, Yongmin
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p. 588 - 589
(2007/10/03)
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- A convenient method for the synthesis of β,γ-unsaturated sulfones through zinc-mediated C-S coupling reaction
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Through zinc-mediated coupling reaction of allylic bromides with alkane- or arenesulfonyl chlorides, β,γ-unsaturated sulfones were obtained with moderate to good yields.
- Sun, Peipei,Wang, Lei,Zhang, Yongmin
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p. 5549 - 5550
(2007/10/03)
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- On the mechanism of the reaction of α-substituted ketones with allyltributylstannane
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The mechanisms for the reaction of allyltributylstannane with a number of fragmentation probes, α-substituted acetophenones, were studied. All reactions were shown to proceed through free radical chain sequences since they could be initiated by AIBN and inhibited by m-dinitrobenzene (DNB). α-Halo- and α-(benzoyloxy)acetophenones (I and II, PhCOCR1R2X; X = F, Cl, Br, OCOPh; R1, R2 = H, Me) yielded the allylation products, PhCOCR1R2CH2CH=CH2), through a chain sequence involving as the propagation step: an electron transfer from Bu3Sn? to I and II, fragmentation of the ketyl anion PhCOCR1R2X?-, and addition of PhCOCR1R2? to allyltributylstannane. The reactions of α-(arylsulfonyl)acetophenones (IIIa-c, PhCOCR1R2Y, Y = SO2Tol-p), however, gave a nearly 1:1 mixture of allyl tosyl sulfone and the corresponding ketone, PhCOCHR1R2. The 1H and 13C NMR of the reaction mixture between allyltributylstannane and α-(p-methylbenzenesulfonyl)-isobutyrophenone substantiated the intermediacy of the tin enolate PhC(OSnBu3)=CMe2. These results suggested that a radical addition elimination mechanism was involved in the reactions of IIIa-c with allylstannane. The reaction of α-phenylthioacetophenone (IV, PhCOCH2SPh) gave both the electron transfer and the addition elimination products (PhCOCH2CH2CH=CH2, Ph-COCH3), indicating that both pathways were involved in the formation of the products.
- Li, Xianfeng,Chen, Jian J.,Tanner, Dennis D.
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p. 4314 - 4318
(2007/10/03)
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- Radical-chain reactions of sulfonyl azides and of ethyl azidoformate with allylstannanes: Homolytic allylation at nitrogen
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4-Methylbenzenesulfonyl azide reacts with allyltriphenylstannane (ATPS) in refluxing benzene, in the presence of 2,2′-azobis(2-methylpropionitrile) as initiator, to give N-allyl-4-methylbenzenesulfonamide in good yield after hydrolytic work-up. Small amounts of allyl 4-methylphenyl sulfone were also formed. The reaction follows a free-radical chain mechanism which involves competitive addition of Ph5Sn? to Na and to Nc of the azido group in ArSO2NaNbNc. Addition to Na followed by loss of nitrogen gives ArSO2NSnPh3, the precursor of the N-allylarenesulfonamide, while addition to Nc leads to the formation of ArSO2 and thence to the allyl aryl sulfone. Allyltrimethylstannane behaves in a similar way to ATPS, but allyltributylstannane gives only a low yield of N-allylarenesulfonamide and the major product is the unsubstituted sulfonamide MeC6H4SO2NH2, which results because the radical ArSO2NSnBu3 undergoes intramolecular 1,5-hydrogen-atom transfer in preference to adding to the allylstannane. 2-Methylallyltriphenylstannane reacts in an analogous way to ATPS, but allylstannanes containing non-terminal double bonds do not react successfully. The arenesulfonyl azides 4-XC6H4SO2N3 (X = H, MeO, F) react in a similar way to tosyl azide, but the reaction is very sluggish when X = NO2? With 1-octanesulfonyl azide, reaction with Ph3Sn? is much less selective and products arising from attack at Na and Nc are formed in comparable yields. Ethyl azidoformate reacts with allylstannanes in a similar manner to, although more slowly than, tosyl azide and gives good yields of the corresponding allylic carbamates.
- Dang, Hai-Shan,Roberts, Brian P.
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p. 1493 - 1498
(2007/10/03)
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- Phase-Transfer Catalytic (PTC) Chlorination of Allylic Sulphones
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Phase-transfer catalytic reactions of allylic sulphones with hexachloroethane or carbon tetrachloride afford mono- or dichlorinated products, with high yields. - Key words: phase transfer catalysis (PTC); allylic sulphones; halogenophilic reaction
- Jonczyk, A.,Radwan-Pytlewski, T.
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p. 1422 - 1427
(2007/10/03)
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- Electrophilic allylation of arenes with in situ generated allyltriarylbismuthonium compound: The Bismuth-mediated polarity inversion of allylsilanes
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Reaction of triarylbismuth difluorides 1 with allyltrimethylsilane 2 in CH2Cl2 in the presence of BF3·OEt2 at low temperature generates allyltriarylbismuthonium compound 3 as a pale yellow solution, in which aromatic hydrocarbons and ethers, triphenylphosphine, dimethyl sulfide, p-toluenesulfinate, and thiophenol are all readily allylated to afford the corresponding allyl derivatives in moderate to good yields.
- Matano, Yoshihiro,Yoshimune, Masanori,Suzuki, Hitomi
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p. 7475 - 7478
(2007/10/02)
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- Sulfonylation of Organometallic Reagents with Arenesulfonyl Fluorides: A Simple One-Step Synthesis of Sulfones
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Sulfonylation of organometallic reagents was accomplished with arenesulfonyl fluorides to provide a wide variety of alkylaryl- and diaryl sulfones.Organolithium and diorganocopper lithium reagents react smoothly with arenesulfonyl fluorides to give sulfones in high yields.Alkyl Grignard reagents often lead to mixtures of monosulfonylated and disulfonylated products.However, allylmagnesium chloride and phenylmagnesium chloride provide the corresponding sulfones in excellent yields.Organocopper reagents were also found to yield sulfones upon treatment with arenesulfonyl fluorides.By utilizing this methodology, synthetically useful alkyl, (trimethylsilyl)methyl, and allyl sulfones are easily prepared in high yields.
- Frye, Leah L.,Sullivan, Eileen L.,Cusack, Kevin P.,Funaro, John M.
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p. 697 - 701
(2007/10/02)
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- Efficient synthesis of sulphones using polysorbate-80 as phase transfer catalyst
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A very easy and practical method of preparing sulphones from alkyl halides has been developed using Polysorbate-80 as phase transfer catalyst.
- Biswas, Goutam K,Chakrabarty, Manas,Bhattacharyya, Prantosh
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- SH2' Type Reactions of Arenesulfonyl Chlorides with Allylic Compounds Catalyzed by a Ruthenium(II) Complex
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In the presence of a catalytic amount of dichlorotris(triphenylphosphine)ruthenium(II), the reactions of arenesulfonyl chlorides with allyl phenyl sulfide and allyl phenyl selenide proceeded smoothly to give allyl phenyl sulfone in high yield as well as the corresponding diphenyl disulfide or diphenyl diselenide.An SH2'-type mechanism involving the arenesulfonyl radical is proposed.
- Kamigata, Nobumasa,Ishii, Kimiko,Ohtsuka, Takeshi,Matsuyama, Haruo
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p. 3479 - 3481
(2007/10/02)
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- A simple and rapid preparation of sulfones from alkyl halides using ultrasound
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Appropriate alkyl halides and sodium p-toluenesulfinates react rapidly in DMF-water at room temperature under the influence of ultrasound to afford sulfones. Using this procedure a wide variety of sulfones have been prepared.
- Biswas,Jash,Bhattacharyya
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p. 491 - 492
(2007/10/02)
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- RADICAL CHAIN CYCLIZATION OF ALLYLIC COMPOUNDS
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The light induced additions of tosyl iodide and tosyl bromide to some diallylic compounds and dienes are studied.Cyclization occurs in some cases but the yields are quite small.Results are discussed on the grounds of free radical cyclization.
- Serra, A.C.,Silva Correa, C.M.M. da,Vieira, M.A.M.S.A.,Gomes, M.A.
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p. 3061 - 3070
(2007/10/02)
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- Substituted Lithium (E)-3-Lithio-3-tosyl-2-propenolates: Useful Intermediates in Organic Synthesis
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The lithiation of substituted tosylated epoxides 7 derived from allylic sulfones with methyllithium leads to lithium (E)-3-lithio-3-tosyl-2-propenolates 5 in a stereoselective manner.The further reaction of these intermediates with different electrophilic
- Najera, Carmen,Yus, Miguel
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p. 1491 - 1499
(2007/10/02)
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- INDUCTION PAR LA LUMIERE DE L'OXYDATION DES COMPLEXES Η3-ALLYLPALLADIUM PAR L'OXYGENE MOLECULAIRE
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Irradiation at λ=366 nm of oxygenated solutions of η3-allylpalladium complexes leads to unsaturated carbonyl compounds.Substitution of the η3-allyl ligand by an electron withdrawing group could induce a regioselective oxidation of the allylic position farthest from this group.The efficiency of these reactions is sensible to the nature of the solvent.
- Muzart, J.,Pale, P.,Pete, J.P.,Riahi, A.
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p. 731 - 739
(2007/10/02)
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- Palladium-catalyzed allylic oxidation of 1-(p-toluenesulfonyl)-2-propene and 1-(trimethylsilyl)-1-(p-toluenesulfonyl)-2-propene
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The course of palladium-catalyzed oxidation of a terminal alkene by t-BuOOH or by O2/H2O is greatly modified when the allylic carbon bears a p-toluenesulfonyl substituent, and allylic oxidation results.Mechanistic explanations of this observation are prop
- Muzart, Jacques,Pete, Jean-Pierre,Riahi, Abdelkhalek
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p. 113 - 120
(2007/10/02)
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- Studies on Chiral Organo-Sulfur Compounds. II. Stereochemistry of Thermal Chiral Allyl Sulfinate-Sulfone Rearrangements
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A highly efficient and general synthetic route to optically active sulfinates by the stereospecific boron trifluoride etherate-catalyzed esterification of sulfinamides was developed.Dramatic solvent effects were observed in the thermal transformation of allyl sulfinate derivatives to sulfones.Heating of chiral trans- and cis-allyl sulfinates, (S)-(-)-3a,c,e and (S)-(-)-3b,d,f, in N,N-dimethylformamide at 90-120 deg C provided chiral sulfones (S)-(+)- and (R)-(-)-5,6,7 in good yields, respectively, with exceedingly high stereospecificity. Keywords - asymmetric transfer; stereospecificity; chiral allyl sulfinate; chiral allyl sulfone; boron trifluoride etherate; thermolysis
- Hiroi, Kunio,Kitayama, Ryuichi,Sato, Shuko
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p. 2628 - 2638
(2007/10/02)
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- ASYMMETRIC SYNTHESIS OF CHIRAL SULFOXIDES VIA MICROBIAL OXIDATION OF SULFIDES
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Incubation of alkyl aryl and allyl aryl sulfides with growing cells of Corynebacterium equi IFO 3730 gave the corresponding optically active sulfoxides with high enantiomeric excess.
- Ohta, Hiromichi,Okamoto, Yashushi,Tsuchihashi, Gen-ichi
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p. 205 - 208
(2007/10/02)
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