- A Simplified Protocol for the Stereospecific Nickel-Catalyzed C-S Vinylation Using NiX 2 Salts and Alkyl Phosphites
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A Ni-catalyzed C-S cross-coupling using only NiI 2 (0.5-2.5 molpercent) and P(O i Pr) 3 (2.0-10.0 molpercent) is reported. Using an air-stable Ni(II) precatalyst, and a cheap and commercially available ligand, a scalable and robust method was developed to cross-couple various thiophenols and styryl bromides, including some sterically encumbered thiols, an α-bromocinnamaldehyde as well as a thiolation-cyclization.
- Larin, Egor M.,Lautens, Mark,Marchese, Austin D.,Mirabi, Bijan
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p. 311 - 319
(2019/12/28)
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- Electrophilic Vinylation of Thiols under Mild and Transition Metal-Free Conditions
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The iodine(III) reagents vinylbenziodoxolones (VBX) were employed to vinylate a series of aliphatic and aromatic thiols, providing E-alkenyl sulfides with complete chemo- and regioselectivity, as well as excellent stereoselectivity. The methodology displays high functional group tolerance and proceeds under mild and transition metal-free conditions without the need for excess substrate or reagents. Mercaptothiazoles could be vinylated under modified conditions, resulting in opposite stereoselectivity compared to previous reactions with vinyliodonium salts. Novel VBX reagents with substituted benziodoxolone cores were prepared, and improved reactivity was discovered with a dimethyl-substituted core.
- Castoldi, Laura,Di Tommaso, Ester Maria,Gr?fen, Barbara,Olofsson, Berit,Reitti, Marcus
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supporting information
p. 15512 - 15516
(2020/06/23)
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- Safe and Metal-Free Synthesis of 1-Alkenyl Aryl Sulfides and Their Sulfones from Thiiranes and Diaryliodonium Salts
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A series of 1-alkenyl aryl sulfides was synthesized from thiiranes and diaryliodonium salts in tetrahydrofuran in the presence of potassium tert -butoxide. The proposed reaction mechanism involves generation of benzynes from the diaryliodonium salts in the presence of the base. Then, nucleophilic attack of the benzynes by thiiranes, followed by hydrogen abstraction and ring opening of the generated thiiranium intermediates, provides the sulfides. These sulfides were further oxidized with performic acid to the corresponding sulfones. The current method provides a metal-free and safe method for the preparation of 1-alkenyl aryl sulfides and their sulfones.
- Dong, Jun,Xu, Jiaxi
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p. 2407 - 2415
(2018/04/16)
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- Alkenyl preparation method of sulfide
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The invention discloses a method for preparing alkenyl sulfide. The method comprises the following steps: adding a styrene derivative of the formula I as shown in the specification into a disulfide compound of the formula II as shown in the specification,
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Paragraph 0038-0040
(2017/03/23)
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- Decarbonylation of Salicylaldehyde Activated by p-Cymene Ruthenium(II) Dimer: Implication for Catalytic Alkyne Hydrothiolation
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A stoichiometric C–H activation/decarbonylation of salicylaldehyde by [(η6-p-cymene)RuCl2]2gave a carbonyl derivative [(η6-p-cymene)RuCl(CO)(Ph-O)] (1) without the use of CO gas. A variety of polar phosphines were then incorporated into compound 1 to give new RuIIcationic catalysts, [(η6-p-cymene)Ru(CO)(Ph-O)L]BF4(2–8). These were used to catalyse the hydrothiolation of alkynes with a range of thiols in aqueous THF to give anti-Markovnikov E-linear vinyl sulfides in high yields.
- Modem, Sarangapani,Kankala, Shravankumar,Balaboina, Ramesh,Thirukovela, Narasimha Swamy,Jonnalagadda, Sreekantha B.,Vadde, Ravinder,Vasam, Chandra Sekhar
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p. 4635 - 4642
(2016/09/28)
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- Copper-mediated stereospecific C-H oxidative sulfenylation of terminal alkenes with disulfides
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A copper and iodine-mediated C-H oxidative sulfenylation of olefins with diaryl disulfides has been developed for the stereospecific synthesis of vinyl thioether. With the combination of Cu(OTf)2 and I2, a variety of terminal alkenes
- Tu, Hai-Yong,Hu, Bo-Lun,Deng, Chen-Liang,Zhang, Xing-Guo
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supporting information
p. 15558 - 15561
(2015/10/28)
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- Thiol-ene "click" reaction triggered by neutral ionic liquid: The "ambiphilic" character of [hmim]br in the regioselective nucleophilic hydrothiolation
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Thiol-ene "click" chemistry has emerged as a powerful strategy to construct carbon-heteroatom (C-S) bonds, which generally results in the formation of two regioisomers. To this end, the neutral ionic liquid [hmim]Br has been explored as a solvent cum catalyst for the synthesis of linear thioethers from activated and inactivated styrene derivatives or secondary benzyl alcohols and thiols without the requirement of using a metal complex, base, or free radical initiator. Furthermore, detailed mechanistic investigations using 1H NMR spectroscopy and quadrupole time-of-flight electrospray ionization mass spectrometry (Q-TOF ESI-MS) revealed that the "ambiphilic" character of the ionic liquid promotes the nucleophilic addition of thiol to styrene through an anti-Markovnikov pathway. The catalyst recyclability and the extension of the methodology for thiol-yne click chemistry are additional benefits. A competitive study among thiophenol, styrene, and phenyl acetylene revealed that the rate of reaction is in the order of thiol-yne a?a thiol-ene a?a dimerization of thiol in [hmim]Br.
- Kumar, Rajesh,Saima,Shard, Amit,Andhare, Nitin H.,Richa,Sinha, Arun K.
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supporting information
p. 828 - 832
(2015/02/05)
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- Highly stereoselective anti-Markovnikov hydrothiolation of alkynes and electron-deficient alkenes by a supported Cu-NHC complex
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A practical, efficient, and low-cost heterogeneous catalyst consisting of a Cu-NHC (N-heterocyclic carbene) complex grafted to SBA-15 silica for the catalytic hydrothiolation of alkynes and electron-deficient alkenes under mild reaction conditions has been developed. The heterogeneous catalyst displays higher activity and stereoselectivity to Z-anti-Markovnikov isomers compared with the homogeneous analog under otherwise identical reaction conditions. The catalytic system is applicable to a broad range of alkynes and thiols and is recyclable without significant loss in catalytic performance. High activity and perfect selectivity to alkyl sulfides formed by the addition of electron-deficient alkenes to various thiols catalyzed by the supported Cu-NHC complex were also realized. This journal is the Partner Organisations 2014.
- Yang, Yong,Rioux, Robert M.
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p. 3916 - 3925
(2014/08/05)
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- Amino acid and water-driven tunable green protocol to access S-S/C-S bonds via aerobic oxidative coupling and hydrothiolation
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A green methodology utilizing a natural supplement such as l-arginine in conjunction with water and oxygen led to oxidative coupling of thiols into disulfides (S-S bond) whereas thiol-yne coupling to access vinyl sulfides (C-S bond) was facilitated in a nitrogen atmosphere. The tunable protocol offers several advantages such as low catalyst loading, high yields, clean reaction, no over-oxidation of the S-S bond besides being metal/base/waste-free. The synthesis of ubiquitous cystine and glutathione disulfide in the same catalytic system is an added advantage and the catalytic system has been recycled up to seven times. the Partner Organisations 2014.
- Shard, Amit,Kumar, Rajesh,Saima,Sharma, Nidhi,Sinha, Arun K.
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p. 33399 - 33407
(2014/08/18)
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- Cu(i)-catalyzed aerobic cross-dehydrogenative coupling of terminal alkynes with thiols for the construction of alkynyl sulfides
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Highly active and selective aerobic cross-dehydrogenative coupling of terminal alkynes with thiols to construct alkynyl sulfides catalyzed by Cu(i) using molecular oxygen as the oxidant has been demonstrated under mild reaction conditions. The process is applicable to a wide range of alkynes and various thiols and is compatible with a variety of functional groups on both alkyne and thiol coupling partners.
- Yang, Yong,Dong, Weibing,Guo, Yisong,Rioux, Robert M.
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supporting information
p. 3170 - 3175
(2013/11/06)
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- Glycerol/CuI/Zn as a recyclable catalytic system for synthesis of vinyl sulfides and tellurides
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A convenient approach to the Cu-catalyzed coupling of diphenyl disulfide and diphenyl ditelluride with vinyl bromides using a recyclable catalytic system and glycerol as a green solvent is described. This protocol was efficiently used in the preparation of vinyl sulfides and vinyl tellurides with a variety of substituents in good yields and stereoselectively. The solvent/catalyst system was directly reused for four cycles without loss of activity.
- Gon?alves, Lóren C.C.,Lima, David B.,Borba, Pedro M.Y.,Perin, Gelson,Alves, Diego,Jacob, Raquel G.,Lenard?o, Eder J.
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p. 3475 - 3480
(2013/07/05)
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- Carbon dioxide mediated stereoselective copper-catalyzed reductive coupling of alkynes and thiols
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A simple protocol for the stereoselective copper-catalyzed hydrothiolation of alkynes under a CO2 atmosphere has been developed. The stereoselectivity is determined by the presence/absence of a CO2 atmosphere. The reaction system is robust and utilizes inexpensive, readily available substrates. A cyclic alkene/carboxylate copper complex intermediate is proposed as the key step in determining the stereoselectivity, and an equivalent amount of water is found to play an active role as a proton donor.
- Nurhanna Riduan, Siti,Ying, Jackie Y.,Zhang, Yugen
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supporting information; experimental part
p. 1780 - 1783
(2012/06/04)
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- Heterogeneous hydrothiolation of alkynes with thiols catalyzed by diphosphino-functionalized MCM-41 anchored rhodium complex
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A novel diphosphino-functionalized MCM-41 anchored rhodium complex [MCM-41-2P-RhCl(PPh3)] was conveniently synthesized by the reaction of diphosphino-functionalized MCM-41 (MCM-41-2P) with RhCl(PPh3) 3. It was found that this rhodium complex is an efficient catalyst for the hydrothiolation of terminal alkynes with thiols and can be recovered and recycled by a simple filtration of the reaction solution and used for at least ten consecutive trials without any decreases in activity.
- Zhao, Hong,Peng, Jian,Cai, Mingzhong
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experimental part
p. 138 - 142
(2012/03/11)
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- Highly regio- and stereoselective hydrothiolation of acetylenes with thiols catalyzed by a well-defined supported Rh complex
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Highly regio- and stereoselective hydrothiolation of a wide range of alkynes with various thiols was demonstrated in the presence of a well-defined Rh complex supported on mesoporous SBA-15 silica. The catalyst was easily recovered and reused several times without significant loss of activity or selectivity.
- Yang, Yong,Rioux, Robert M.
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supporting information; experimental part
p. 6557 - 6559
(2011/06/28)
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- Recyclable nano copper oxide catalyzed stereoselective synthesis of vinyl sulfides under ligand-free conditions
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A simple and efficient protocol for the cross-coupling of vinyl halides with thiols catalyzed by recyclable CuO nanoparticles under ligand-free conditions is reported. This methodology results in the synthesis of a variety of vinyl sulfides in excellent y
- Reddy, Vutukuri Prakash,Swapna, Kokkirala,Kumar, Akkilagunta Vijay,Rao, Kakulapati Rama
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experimental part
p. 2783 - 2788
(2010/03/03)
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- Radical-mediated thiodesulfonylation of the vinyl sulfones: access to (α-fluoro)vinyl sulfides
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Radical-mediated thiodesulfonylation of the vinyl and (α-fluoro)vinyl sulfones, derived from aldehydes and ketones, with aryl thiols in organic or aqueous medium provided access to vinyl and (α-fluoro)vinyl sulfides. The vinyl sulfides were formed predominantly with E stereochemistry independent of the stereochemistry of the starting vinyl sulfones.
- Sacasa, Pablo R.,Zayas, Jessica,Wnuk, Stanislaw F.
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experimental part
p. 5424 - 5427
(2009/12/06)
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- Mild Copper(I) iodide/β-keto ester catalyzed coupling reactions of styryl bromides with phenols, thiophenols, and imidazoles
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An efficient and mild vinylation of O-, S-, and N-nucleophiles is reported. Copper(I) iodide/ethyl 2-oxocyclohexanecarboxylate is used as the catalytic system. The protocol tolerates a broad range of functional groups on the substrates, and gives the corr
- Bao, Weiliang,Liu, Yunyun,Lv, Xin
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experimental part
p. 1911 - 1917
(2009/04/04)
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- A simple and general preparation of vinylic sulfides, selenides and tellurides
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A general method for the synthesis of vinylic chalcogenides by nucleophilic and Ni-catalyzed vinylic substitution on vinylic halides by phenyl chalcogenolates is described. The reactions were regio and stereoselective for the nickel catalyzed substitution
- Silveira, Claudio C.,Santos, Paulo Cesar S.,Mendes, Samuel R.,Braga, Antonio L.
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scheme or table
p. 3787 - 3790
(2009/04/06)
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- Hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide: selective synthesis of (Z)-1-alkenyl sulfides and selenides
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A simple, stereoselective and efficient method for the hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide has been developed. In the presence of CuI, rongalite, and Cs2CO3, a variety of disulfides underwent the reaction of terminal alkynes stereoselectively to afford the corresponding (Z)-1-alkenyl sulfides in moderate to excellent yields. It is noteworthy that hydroselenations of 1,2-diphenyldiselane with alkynes are also conducted smoothly to afford (Z)-1-alkenyl selenides in good yields under the standard conditions.
- Wang, Zhang-Lin,Tang, Ri-Yuan,Luo, Pei-Song,Deng, Chen-Liang,Zhong, Ping,Li, Jin-Heng
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p. 10670 - 10675
(2008/12/23)
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- L-Proline promoted cross-coupling of vinyl bromide with thiols catalyzed by CuBr in ionic liquid
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A method for the synthesis of vinyl sulfides by the coupling of vinyl bromides with thiols using the copper(I) bromide as catalyst and l-proline as ligand was reported. The best yields were obtained in the ionic liquid [Bmim]BF4 with the retention of stereochemistry. This protocol is palladium-free, tolerates both aromatic and aliphatic thiols, possesses good selectivity between alcohol and thiol, and does not require the use of expensive or air-sensitive additives.
- Zheng, Yunfa,Du, Xingfen,Bao, Weiliang
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p. 1217 - 1220
(2007/10/03)
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- Stereoselective synthesis of E-vinyl sulfides from alkynes in water under neutral conditions using β-cyclodextrin
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This is the first example of stereoselective synthesis of E-vinyl sulfides in water in excellent yields by hydrothiolation of aromatic alkynes with thiophenols by anti-Markonikov addition in the presence of β-cyclodextrin. This protocol tolerates a wide v
- Sridhar,Surendra,Srilakshmi Krishnaveni,Srinivas,Rama Rao
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p. 3495 - 3497
(2007/10/03)
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- Synthesis of ketene (S, Te) acetals and their transformation into Z-α- phenylthio-α,β-unsaturated aldehydes
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Reaction of thiomethyl phosphonates with aryl (or butyl) tellurenyl halides and aldehydes under basic conditions provides moderate to good yields of ketene thio (telluro) acetals, with vinylic sulfides being byproducts of this transformation. Tellurium-li
- Silveira, Claudio C.,Perin, Gelson,Braga, Antonio L.,Dabdoub, Miguel J.,Jacob, Raquel G.
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p. 7421 - 7432
(2007/10/03)
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- Highly regio- and stereocontrolled synthesis of vinyl sulfides via transition-metal-catalyzed hydrothiolation of alkynes with thiols
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Regio- and stereoselectivity in the hydrothiolation of alkynes with thiols in the presence of a variety of transition-metal catalysts is investigated in detail. Among the catalysts employed, RhCl(PPh3)3 exhibits excellent catalytic ability toward the anti-Markovnikov addition of thiols (ArSH) to alkynes (RC≡CH), which affords the corresponding vinylic sulfides (trans-RCH=CHSAr) regio- and stereoselectively. The reaction may proceed by the formation of hydrorhodium sulfide species (H-[Rh]-SAr) and probably via the subsequent hydrorhodation of alkynes to provide vinylrhodium intermediates (RCH=CH-[Rh]-SAr). In contrast, PdCl2(PhCN)2-catalyzed hydrothiolation of aromatic alkynes (ArC≡CH) takes place to give the corresponding Markovnikov adducts (R(ArS)C=CH2) with excellent regioselectivity, probably via thiopalladation of alkynes by palladium sulfide species (ArS-[Pd]-Cl), which may be formed by ligand-exchange reaction between PdCl2(PhCN)2 and ArSH. Furthermore, in the case of alkynes bearing propargylic protons (R'CH2C≡CH), a sequential addition/isomerization reaction occurs to provide the internal vinylic sulfides (R'CH=C(SAr)CH3) regioselectively. From the same starting materials (alkyne and thiol), therefore, the regioselectivity of hydrothiolation can be attained simply by changing the catalysts, i.e., RhCl(PPh3)3 and PdCl2(PhCN)2.
- Ogawa, Akiya,Ikeda, Takuma,Kimura, Kouichi,Hirao, Toshikazu
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p. 5108 - 5114
(2007/10/03)
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- Mn(III)-based reactions of alkenes and alkynes with thiols. An approach toward substituted 2,3-dihydro-1,4-oxathiins and simple route to (E)-vinyl sulfides
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The first example using manganese(III) acetate in the reaction of 1,1- diarylethenes with α-mercaptoketones was examined. A mixture of the ethenes and α-mercaptoketones was treated with manganese(III) acetate in acetic acid, affording cycloaddition products in moderate yields, together with substituted products. The reaction may involve the formation of a carbonation and subsequent cyclization to give the substituted 2,3-dihydro-1,4-oxathiin 3. A similar reaction with thioglycolic acid gave 1,4-oxathiolan-2-one 7. While thiyl radicals easily formed by manganese(III) oxidation with ethanethiol or benzenethiol reacted with alkynes to give preferentially (E)- vinyl sulfides 10 in quantitative yields.
- Nguyen, Van-Ha,Nishino, Hiroshi,Kajikawa, Shougo,Kurosawa, Kazu
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p. 11445 - 11460
(2007/10/03)
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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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- Homologation of aldehydes using (phenylthiomethylene) triphenylarsorane: Selective preparation of α-thiophenoxyepoxides and phenylthioenol ethers
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The title arsonium ylide reacts with aldehydes to give exclusively α-thiophenoxyepoxides in THF and phenylthioenol ethers in THF/HMPA. The former adducts are readily transformed to α-thiophenoxy carbonyls and the latter to one-carbon homologated aldehydes.
- Boubia,Mioskowski,Manna,Falck
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p. 6023 - 6026
(2007/10/02)
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