- Palladium-triethylborane-triggered direct and regioselective conversion of allylic alcohols to allyl phenyl sulfones?
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A combination of Pd(OAc)2 (5 mol %), PPh3 (10 mol %), and Et3B (200 mol %) promotes the formation of allyl phenyl sulfones from the allylic alcohols directly with excellent yields under mild conditions. The activation of an alcohol group is not necessary which is achieved in situ. The conjugated dienols also were equally effective for the said transformation.
- Chandrasekhar, Srivari,Jagadeshwar, Vannada,Saritha, Birudaraju,Narsihmulu, Cheryala
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- 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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- Reciprocal-Activation Strategy for Allylic Sulfination with Unactivated Allylic Alcohols
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A reciprocal-activation strategy for allylic sulfination with unactivated allylic alcohols was developed. In this reaction, the hydrogen bond interaction between allylic alcohols and sulfinic acids allowed for reciprocal activation, which enabled a dehydrative cross-coupling process to occur under mild reaction conditions. This reaction worked in an environmentally friendly manner, yielding water as the only byproduct. A variety of allylic sulfones could be obtained in good to excellent yields with wide functional group tolerance. In gram scale reactions, allylic sulfones could be conveniently isolated in high yield by filtration.
- Xie, Peizhong,Sun, Zuolian,Li, Shuangshuang,Cai, Xinying,Qiu, Ju,Fu, Weishan,Gao, Cuiqing,Wu, Shisheng,Yang, Xiaobo,Loh, Teck-Peng,Loh, Teck-Peng
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supporting information
p. 4893 - 4897
(2020/06/24)
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- Vinylethylene Carbonates as α,β-Unsaturated Aldehyde Surrogates for Regioselective [3 + 3] Cycloaddition
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Herein, we report a novel stepwise addition-controlled ring size method, to access tetrahydropyrimidines through an operationally simple [3 + 3] cycloaddition of vinylethylene carbonates with triazinanes. Interestingly, we could also use this method for a [3 + 3] oxidative cycloaddition, which allows the facile synthesis of polysubstituted terphenyls under mild conditions. Mechanistic studies suggest that vinylethylene carbonates could generate α,β-unsaturated aldehydes as 3-carbon synthons for cycloaddition via a combination process of Pd-catalyzed decarboxylation and β-H elimination.
- Xu, Yi,Chen, Lu,Yang, Yu-Wen,Zhang, Zhiqiang,Yang, Weibo
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supporting information
p. 6674 - 6678
(2019/09/03)
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- Allyl sulfone compound and preparation method and application thereof
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The invention discloses an allyl sulfone compound and a preparation method and application thereof. The preparation method comprises the following steps of sequentially adding allyl alcohol, sulfinicacid, palladium tetrakis(triphenylphosphine) and calcium bis(trifluoromethylsulfonyl)imide into a reaction solvent in an inert gas atmosphere, and carrying out a reaction under stirring for 12-48 h atthe temperature of 30 DEG C, wherein the equivalent ratio of allyl alcohol, sulfinic acid, palladiumtetrakis(triphenylphosphine) and calcium bis(trifluoromethylsulfonyl)imide is 1: (1.5-2): (1-3%): (5-10%); and removing the reaction solvent in the reaction liquid, and then performingpurifying to obtain the allyl sulfone compound. The preparation method disclosed by the invention is high in economy and wide in applicable substrate range; in addition, the obtained allyl sulfone compound has potential pharmaceutical activity and biological activity and is an important skeleton widely existing inbiologically and pharmaceutically active molecules.
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- Sulfinate-Engaged Nucleophilic Addition Induced Allylic Alkylation of Allenoates
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A strategically novel Pd-catalyzed nucleophilic addition induced allylic alkylation reaction (NAAA) of allenoates has been successfully accomplished. By judiciously integrating ZnCl2-promoted Michael addition with Pd-catalyzed allylic alkylation, allenoates readily undergo allyl-sunfonylation at the internal double bond, thus providing a straightforward avenue for the rapid assembly of a host of structurally diversified α-allyl-β-sufonylbut-3-enoate derivatives. The success of this transformation profits from a delicate control of the reaction kinetic of each elementary step, thanks to the synergistic interaction of Pd/Zn bimetallic system, thus suppressing either direct allylic sulfonylation or premature quenching of therein in situ generated ester enolate intermediate. Furthermore, by expanding the scope of workable Michael acceptor beyond those previously required doubly activated ones, such as methylenemalononitrile, the present work substantially enriches the repertoire of NAAA reactions.
- Lin, Ling-Zhi,Che, Yuan-Yuan,Bai, Peng-Bo,Feng, Chao
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p. 7424 - 7429
(2019/10/02)
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- Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach
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A radical-mediated functionalization of allyl alcohol derived partners with a variety of alkyl 1,4-dihydropyridines via photoredox/nickel dual catalysis is described. This transformation transpires with high linear and E-selectivity, avoiding the requirement of harsh conditions (e.g., strong base, elevated temperature). Additionally, using aryl sulfinate salts as radical precursors, allyl sulfones can also be obtained. Kinetic isotope effect experiments implicated oxidative addition of the nickel catalyst to the allylic electrophile as the turnover-limiting step, supporting previous computational studies.
- Wang, Zheng-Jun,Zheng, Shuai,Romero, Eugénie,Matsui, Jennifer K.,Molander, Gary A.
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supporting information
p. 6543 - 6547
(2019/08/26)
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- Bis(phenylsulfonyl)methane mediated synthesis of olefins: Via a halogen elimination and double bond migration
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An effective dehydrochlorination of bis(phenylsulfonyl)alkane to prepare alkene building blocks is developed. The elimination together with double bond migration results in a variety of β,γ-unsaturated bis(phenylsulfonyl)olefins in good yields with only E geometry. The following chemical diversification represents an easy and straightforward access to a series of alkene building blocks.
- Hu, Yanwei,Jiang, Jing,Hu, Ying,Cai, Xin,Wang, Liudi,Chen, Shaohua,Zhang, Shilei,Zhang, Yinan
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p. 2619 - 2622
(2018/04/27)
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- Alkenylation of C(sp3)?H Bonds by Zincation/Copper-Catalyzed Cross-Coupling with Iodonium Salts
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α-Vinylation of phosphonates, phosphine oxides, sulfones, sulfonamides, and sulfoxides has been achieved by selective C?H zincation and copper-catalyzed C(sp3)?C(sp2) cross-coupling reaction using vinylphenyliodonium salts. The vinylation transformation proceeds in high efficiency and stereospecificity under mild reaction conditions. This zincative cross-coupling reaction represents a general alkenylation strategy, which is also applicable for α-alkenylation of esters, amides, and nitriles in the synthesis of β,γ-unsaturated carbonyl compounds.
- Liu, Chuan,Wang, Qiu
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supporting information
p. 4727 - 4731
(2018/03/21)
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- Oxidative Allylic Esterification of Alkenes by Cooperative Selenium-Catalysis Using Air as the Sole Oxidant
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A new metal-free catalysis protocol for the oxidative coupling of nonactivated alkenes with simple carboxylic acids has been established. This method is predicated on the cooperative interaction of a diselane and a photoredox catalyst, which allows for the use of ambient air or pure O2 as the terminal oxidant. Under the title conditions, a range of both functionalized and nonfunctionalized alkenes can be readily converted into the corresponding allylic ester products with good yields (up to 89%) and excellent regioselectivity as well as good functional group tolerance.
- Ortgies, Stefan,Depken, Christian,Breder, Alexander
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supporting information
p. 2856 - 2859
(2016/07/06)
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- Ring-Closing Metathesis Reactions of Acyloxysulfones: Synthesis of γ-Alkylidene Butenolides
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An acyloxysulfone ring-closing metathesis/sulfone elimination sequence has been developed for the preparation of various γ-alkylidene butenolides. The elimination is proposed to proceed via an E1cb mechanism leading to (Z)-γ-alkylidene butenolides as the major products.
- Phan, Iris T.,Gilbert, Garrett J.,O'Neil, Gregory W.
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supporting information
p. 1867 - 1871
(2015/08/06)
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- Palladium/copper-catalyzed oxidative arylation of terminal alkenes with aroyl hydrazides
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An unprecedented oxidative arylation reaction of terminal alkenes with simple aroyl hydrazides has been developed under aerobic conditions for the stereoselective synthesis of 1,2-disubstituted alkenes. A range of aroyl hydrazides underwent palladium/copper-catalyzed oxidative Mizoroki-Heck reaction with terminal alkenes open to air in a 1:1 mixture of dimethyl sulfoxide and acetonitrile to give structurally diverse 1,2-disubstituted alkenes in moderate to excellent yields with excellent regio- and E-selectivity. The reaction tolerated a wide variety of functional groups, such as alkoxy, hydroxy, amino, fluoro, chloro, bromo, cyano, nitro, ester, amide, imide, phosphine oxide, and sulfone groups, and, moreover, molecular oxygen and dimethyl sulfoxide were demonstrated to serve as terminal oxidants. This study provides a useful method for the stereoselective synthesis of 1,2-disubstituted alkenes through direct transformation of the vinylic Ci-H bonds in terminal alkenes. Cross-coupling: An oxidative arylation reaction of terminal alkenes with simple aroyl hydrazides has been developed in the presence of a PdCl2/CuI catalyst under aerobic conditions to give a range of structurally diverse 1,2-disubstituted alkenes in moderate to excellent yields with excellent regio- and E-selectivity (see scheme; r.s.=regioselectivity).
- Zhang, Yong-Gang,Liu, Xiang-Lei,He, Zeng-Yang,Li, Xi-Ming,Kang, Hong-Jian,Tian, Shi-Kai
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supporting information
p. 2765 - 2769
(2014/03/21)
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- Direct substitution of primary allylic amines with sulfinate salts
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The NH2 group in primary allylic amines was substituted directly by sulfinate salts with excellent regio- and stereoselectivities. In the presence of 0.1 mol % [Pd(allyl)Cl]2, 0.4 mol % 1,4- bis(diphenylphosphino)butane (dppb), and excess boric acid, a range of α-unbranched primary allylic amines were smoothly substituted with sodium sulfinates in an α-selective fashion to give structurally diverse allylic sulfones in good to excellent yields with exclusive E selectivity. Replacing dppb with 1,1′-bi-2-naphthol (BINOL) allowed unsymmetric α-chiral primary allylic amines to be transformed into the corresponding allylic sulfones in good to excellent yields with excellent retention of ee. Importantly, the reaction complements known asymmetric methods in substrate scope via its unique ability to provide α-chiral allylic sulfones with high optical purity starting from unsymmetric allylic electrophiles.
- Wu, Xue-Song,Chen, Yan,Li, Man-Bo,Zhou, Meng-Guang,Tian, Shi-Kai
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supporting information
p. 14694 - 14697
(2012/11/07)
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- An expeditious entry to benzylic and allylic sulfones through byproduct-catalyzed reaction of alcohols with sulfinyl chlorides
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(Chemical Equation Presented) In the absence of external catalysts and additives, a broad range of benzylic and allylic alcohols react with various sulfinyl chlorides to afford structurally diversified benzylic and allylic sulfones in moderate to excellen
- Li, Hai-Hua,Dong, De-Jun,Jin, Yin-Huan,Tian, Shi-Kai
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supporting information; experimental part
p. 9501 - 9504
(2010/03/04)
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- Pincer complex-catalyzed redox coupling of alkenes with lodonium salts via presumed palladium(IV) itermediates
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Palladium pincer complexes directly catalyze the redox coupling reactions of functionalized alkenes and iodonium salts. The catalytic process, which Is suitable for mild catalytic functionalization of allylic acetates and electron-rich alkenes, probably o
- Aydin, Juhanes,Larsson, Johanna M.,Selander, Nicklas,Szabo, Kalman J.
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supporting information; experimental part
p. 2852 - 2854
(2009/12/05)
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- An unexpected reaction of arenesulfonyl cyanides with allylic alcohols: Preparation of trisubstituted allyl sulfones
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(Chemical Equation Presented) An efficient and practical protocol for the highly selective preparation of substituted allyl sulfones has been developed. Arenesulfonyl cyanides, Baylis-Hillman adducts, and simple allylic alcohols give an unforeseen outcome
- Reddy, Leleti Rajender,Hu, Bin,Prashad, Mahavir,Prasad, Kapa
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experimental part
p. 172 - 174
(2009/04/10)
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- π-Allylic sulfonylation in water with amphiphilic resin-supported palladium-phosphine complexes
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π-Allylic substitution of allyl esters with sodium arylsul-finate was performed with an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported phosphine-palladium complex in water as a single reaction medium under heterogeneous conditions to give allyl sulfones in good to high yields. Catalytic asymmetric allylic substitution of cycloalkenyl esters also took place in water using a PS-PEG resin-supported chiral imidazo-indolephosphine- palladium complex to give cycloalkenyl sulfones with up to 81% ee.
- Uozumi, Yasuhiro,Suzuka, Toshimasa
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experimental part
p. 1960 - 1964
(2009/04/04)
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- Reduction of propargylic sulfones to (Z)-allylic sulfones using zinc and ammonium chloride
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Propargylic sulfones can be cis-hydrogenated using commercial zinc powder and ammonium chloride in THF-water at room temperature, the major products being the corresponding (Z)-allylic sulfones. Other reducible groups (alkene, benzyloxy) are not affected. Allenylsulfones are implicated in one of the possible reaction pathways.
- Sheldrake, Helen M.,Wallace, Timothy W.
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p. 4407 - 4411
(2008/02/03)
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- Novel model sulfur compounds as mechanistic probes for enzymatic and biomimetic oxidations
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To test for the intermediacy of sulfide radical cations in biomimetic and enzymatic oxidations, the sulfides PhSCH3 (1a), PhSCH2Ph (1b), PhSCHPh2 (1c), PhSCPh3 (1d), CH 3SCHPh2 (2), PhSCH2CH=CH2 (3), PhSCH2CH=CHPh (4) and CH3SCH2CH=CHPh (5) were studied, and their results were compared to those obtained for the corresponding chemical electron transfer (CET) and photoinduced electron transfer (PET) oxidations. The radical cations generated from 3-5 by CET in the presence of cerium(IV) ammonium nitrate (CAN) yielded only fragmentation products from the alkyl cations and the thiyl radicals (RS.), whereas 2.+ afforded both fragmentation and mainly α-deprotonation products. Photochemical treatment of the sulfides 1a and 1b with C(NO2) 4 gave only the corresponding sulfoxides, while fragmentation was the main pathway for the photoreactions of 1c, 2 and 5, and for 1d only this latter process was observed. These results support our selection of the sulfides RSCHPh2, RSCH2CH=CHPh (R = Me, Ph) and PhSCPh3 as models for the biomimetic and enzymatic studies. As evidenced by the sulfoxides and sulfones detected as unique products both in protic and in aprotic solvents, it is proposed that the mechanism of the biomimetic sulfoxidations of sulfides 1c and 2-5 by TPPFeIIICI is direct oxygen transfer. Three enzymes - Coprinus cinereus peroxidase (CiP), horseradish peroxidase (HRP) and chloroperoxidase (CPO) - were studied in the oxidation of sulfides 1a, 2, 4 and 5. The use of a racemic alkyl hydroperoxide in the CiP enzymatic oxidation of sulfides 5 and 2 yielded the corresponding sulfoxides (23 and 29%) and the aldehyde or benzophenone (5%), respectively. These results suggest the involvement of an ET process for the CiP-catalysed oxidation. Fragmentation products were observed in the enzymatic oxidation of sulfide 4 with HRP, which confirms the previously proposed ET mechanism. On the other hand, the CPO-enzymatic oxidation of sulfide 5 yielded only the corresponding sulfoxide, as would be expected for a direct oxygen-transfer or oxene mechanism. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Penenory, Alicia B.,Argueello, Juan E.,Puiatti, Marcelo
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p. 114 - 122
(2007/10/03)
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- Ionic liquid/water as a recyclable medium for Tsuji-Trost reaction assisted by microwave
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An efficient microwave protocol is described for allylic substitution with various carbon and heteronucleophiles catalyzed by Pd(OAc)2/TPPTS in an [EMIm]BF4/H2O medium. The ionic liquid/water containing catalyst system can be recycled eight times without loss of activity.
- Liao, Meng-Chun,Duan, Xin-Hua,Liang, Yong-Min
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p. 3469 - 3472
(2007/10/03)
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- A versatile and concise route to carbocycles using a 1,6-electrocyclic reaction
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The viability of the 1,6-electrocyclic route to 1,3-cyclohexadienes has been significantly increased by using a phenyl-sulfonyl substituent in a multi-purpose (≥3) role.
- Brandaenge, Svante,Leijonmarck, Hans
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p. 292 - 293
(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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- Integrated Chemical Process: One-Pot Double Elimination Method for Acetylenes
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A novel one-pot process for synthesis of acetylenes has been achieved in which the following series of steps are integrated: addition of an α-anion of sulfone to aldehyde; trapping of the resulting adduct to incorporate a leaving group, and double elimination of this intermediate. Consolidation of Peterson elimination renders the process much simpler. This method provides a convenient and high-yielding access to a variety of enynes and polyynes as well as to functionally substituted aryl acetylenes containing halogen(s) or acetal groups, which are useful building blocks for aryl acetylene scaffolds. Iteration of the one-pot generation of acetylenic bonds provides a new metodology for the buildup of aryl acetylene skeletons.
- Orita, Akihiro,Yoshioka, Naonori,Struwe, Petra,Braier, Arnold,Beckmann, Anke,Otera, Junzo
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p. 1355 - 1363
(2007/10/03)
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- Palladium(0) catalysed rearrangements of allylic sulfoximines to allyl sulfinimidic acid esters and optically active N-Cbz protected γ-amino- enomes
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N-Tosyl allylic sulfoximines undergo rearrangement to allyl sulfinimidic acid esters in the presence of bidentate chiral ligands while N-Cbz allylic sulfoximines give optically active N-Cbz protected γ-amino-enones.
- Pyne, Stephen G.,David, Dorothy M.,Dong, Zemin
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p. 8499 - 8502
(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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- 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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- Tetra-n-butylammonium Oxone. Oxidations under Anhydrous Conditions
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Tetra-n-butylammonium Oxone, readily prepared as a white solid from commercially available Oxone, performs oxidations in anhydrous methylene chloride.Under these conditions, sulfides are oxidized to sulfones in the presence of amines, ketones, esters, car
- Trost, Barry M.,Braslau, Rebecca
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p. 532 - 537
(2007/10/02)
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- Palladium-Catalyzed Substitutions of Allylic Nitro Compounds. Regiochemistry
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Primary, secondary, and tertiary allylic nitro compounds underwent Pd(0)-catalyzed allylic substitution by stabilized carboanions, secondary amines, and benzenesulfinate ion (PhSO2-). α,β-disubstituted α-nitro olefins also behaved as allylic nitro compounds, via base-catalyzed vinyl -> allyl rearrangement, and underwent allylic substitution by secondary amines and PhSO2-.The regiochemistry of these substitutions was dependent on the structure of the allylic nitro compound amd on the steric bulk of the nucleophile.Generally, substitution occurred at the lesshindered or least substituted site.In some cases added or generated NaNO2 affected the regioselectivity of the allylic substitution of allylic nitro compounds and some allylic acetates by PhSO2-.Under these conditions, the more sterically hindered allylic sulfones were formed.
- Tamura, Rui,Kai, Yoshiki,Kakihana, Masato,Hayashi, Koji,Tsuji, Masanori,et al.
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p. 4375 - 4385
(2007/10/02)
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