- (o-Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors
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(o-Phenylenediamino)borylstannanes were newly synthesized to achieve radical boryl substitutions of a variety of alkyl radical precursors. Dehalogenative, deaminative, decharcogenative, and decarboxylative borylations proceeded in the presence of a radica
- Suzuki, Kensuke,Nishimoto, Yoshihiro,Yasuda, Makoto
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supporting information
p. 3968 - 3973
(2020/12/30)
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- Photocatalytic synthesis method of aryl thioether and derivatives thereof
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The invention belongs to the field of organic synthesis, and particularly relates to a photocatalytic synthesis method of aryl thioether and derivatives thereof. The synthesis method comprises the steps: dissolving an N-(sulfanyl) amide compound into a methyl aromatic compound under the protection of inert gas, and thus obtaining the aryl thioether compound under the action of light, a catalyst, aligand and alkali. According to the method, the coupling reaction of a C-S bond is completed through visible light induction by utilizing a light/Ni dual-catalytic system, so that the method has goodfunctional group compatibility, and the C-S bond compound can be selectively and efficiently constructed in one step. The method has the advantages of simple catalytic system, mild reaction conditions, economical, simple and easily available substrate, simple reaction operation and the like.
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-
Paragraph 0084; 0085; 0086; 0087
(2021/04/03)
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- Umpolung Difunctionalization of Carbonyls via Visible-Light Photoredox Catalytic Radical-Carbanion Relay
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The combination of photoredox catalysis with the Wolff-Kishner (WK) reaction allows the difunctionalization of carbonyl groups by a radical-carbanion relay sequence (photo-Wolff-Kishner reaction). Photoredox initiated radical addition to N-sulfonylhydrazones yields α-functionalized carbanions following the WK-type mechanism. With sulfur-centered radicals, the carbanions are further functionalized by reaction with electrophiles including CO2 and aldehydes, whereas CF3 radical addition furnishes a wide range of gem-difluoroalkenes through β-fluoride elimination of the generated α-CF3 carbanions. More than 80 substrate examples demonstrate the broad applicability of this reaction sequence. A series of investigations including radical inhibition, deuterium labeling, fluorescence quenching, cyclic voltammetry, and control experiments support the proposed radical-carbanion relay mechanism.
- Wang, Shun,Cheng, Bei-Yi,Sr?en, Matea,K?nig, Burkhard
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supporting information
p. 7524 - 7531
(2020/08/05)
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- Transition metal-free coupling reactions of benzylic trimethylammonium salts with di(hetero)aryl disulfides and diselenides
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A new protocol was developed to synthesize (enantioenriched) thioethers and selenoethers from (chiral) benzylic trimethylammonium salts and di(hetero)aryl disulfides or diselenides. These syntheses were promoted by the presence of weak base and did not require the use of any transition metal, and resulted in the target products with good to excellent yields (72-94%). Using quaternary ammonium salts synthesized from enantiomerically enriched amines led to highly enantiopure benzylic thioethers and selenoethers (94-99% ee) with configurations reversed from those of their enantioenriched quaternary ammonium salts. This journal is
- Li, Fuhai,Wang, Dan,Chen, Hongyi,He, Ze,Zhou, Lihong,Zeng, Qingle
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p. 13029 - 13032
(2020/11/07)
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- An Iodide-Mediated Transition-Metal-Free Strategy towards Unsymmetrical Diaryl Sulfides via Arylhydrazines and Thiols
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A mild, scalable iodine-mediated oxidative cross-coupling reaction of arylhydrazines and thiols for construction of thioethers (sulfides) in the absence of any transition metals or photocatalysts is disclosed. A variety of unsymmetrical diaryl sulfides with broad substrate scope both on thiols and hydrazines were synthesized in high yields in water at room temperature. Furthermore, to demonstrate the utility of the protocol, the above C-S bond formation was applied in the synthesis of the key structure of vortioxetine as an antidepressant drug. The gram-scale outcome also added to the potential utility of this protocol.
- Asadpour, Mohammad,Azizzade, Meysam,Ghasemi, Mehran,Jafarpour, Farnaz,Rajai-Daryasarei, Saideh
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supporting information
p. 727 - 734
(2020/02/25)
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- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
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Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
- Corma, Avelino,Sorribes, Iván
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p. 3130 - 3142
(2019/03/13)
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- Alkyl Sulfides as Promising Sulfur Sources: Metal-Free Synthesis of Aryl Alkyl Sulfides and Dialkyl Sulfides by Transalkylation of Simple Sulfides with Alkyl Halides
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A site-selective metal-free dealkylative approach to synthesize aryl alkyl and symmetrical dialkyl sulfides has been developed. This procedure is convenient and has wide functional group tolerance giving rise to sulfides carrying various alkyl chains from simple alkyl sulfides and alkyl halides in good to excellent yields. This transalkylation proceeds by an ionic mechanism via sulfonium intermediates and it was proposed that dimethylacetamide (DMAC) may participate in part to promote the reaction.
- Liu, Ting,Qiu, Renhua,Zhu, Longzhi,Yin, Shuang-Feng,Au, Chak-Tong,Kambe, Nobuaki
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supporting information
p. 3833 - 3837
(2018/12/05)
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- Copper(I)-USY as a Ligand-Free and Recyclable Catalyst for Ullmann-Type O-, N-, S-, and C-Arylation Reactions: Scope and Application to Total Synthesis
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The copper(I)-doped zeolite CuI-USY proved to be a versatile, efficient, and recyclable catalyst for various Ullmann-type coupling reactions. Easy to prepare and cheap, this catalytic material enables the arylation and heteroarylation of diverse O-, N-, S-, and C-nucleophiles under ligand-free conditions while exhibiting large functional group compatibility. The facility of this catalyst to promote C-O bond formation was further demonstrated with the total synthesis of 3-methylobovatol, a naturally occurring diaryl ether of biological relevance. From a mechanistic viewpoint, two competitive pathways depending on the nature of the nucleophile and consistent with the obtained results have been proposed.
- Garnier, Tony,Danel, Mathieu,Magné, Valentin,Pujol, Anthony,Bénéteau, Valérie,Pale, Patrick,Chassaing, Stefan
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p. 6408 - 6422
(2018/05/31)
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- Ferromagnetic nanoparticle-supported copper complex: A highly efficient and reusable catalyst for three-component syntheses of 1,4-disubstituted 1,2,3-triazoles and C–S coupling of aryl halides
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A new nanocatalyst was synthesized by immobilization of 4′-(4-hydroxyphenyl)-2,2′:6′,2″-terpyridine/CuI complex on ferromagnetic nanoparticles through a surface modification (FMNPs@SiO2-TPy-Cu). This heterogeneous catalyst was characterized using various techniques including Fourier transform infrared and energy-dispersive X-ray spectroscopies, transmission and scanning electron microscopies, X-ray diffraction, vibrating sample magnetometry and thermogravimetric analysis. The resulting nanocatalyst presented excellent catalytic activity for the regioselective syntheses of 1,4-disubstituted 1,2,3-triazoles and thioethers. The thermally and chemically stable, benign and economical catalyst was easily recovered using an external magnet and reused in at least five successive runs without an appreciable loss of activity.
- Khodaei, Mohammad Mehdi,Bahrami, Kiumars,Meibodi, Farhat Sadat
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- Nano cobalt ferrite catalyzed coupling reaction of nitroarene and alkyl halide: An odorless and ligand-free rout to unsymmetrical thioether synthesis
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This study describes an odorless protocol for the synthesis of unsymmetrical sulfides via cobalt ferrite (CoFe2O4) catalyzed cross-coupling reaction of nitroarenes with alkyl halides in the presence of thiourea as sulfur source under
- Moghaddam, Firouz Matloubi,Pourkaveh, Raheleh
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- Visible-Light-Induced Cyclization of Electron-Enriched Phenyl Benzyl Sulfides: Synthesis of Tetrahydrofurans and Tetrahydropyrans
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A new approach to the preparation of tetrahydrofurans and tetrahydropyrans through a photoredox catalytic process is described. The introduction of a phenylsulfanyl auxiliary group permits the substrates to be readily oxidized to form cationic intermediates for sequential intramolecular cyclization. The method features mild reaction conditions and operational simplicity.
- Li, Wei,Yang, Chao,Gao, Guo-Lin,Xia, Wujiong
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supporting information
p. 1391 - 1396
(2016/06/01)
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- Photosensitized oxidation of aryl benzyl sulfoxides. Evidence for nucleophilic assistance to the c-s bond cleavage of aryl benzyl sulfoxide radical cations
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The radical cations of a series of aryl benzyl sulfoxides (4-X-C6H4CH2SOC6H4Y+?) have been generated by photochemical oxidation of the parent sulfoxides sensitized by 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ+ClO4-). Steady-state photolysis experiments showed the prevailing formation of benzylic products deriving from the C-S fragmentation in the radical cations, together with sulfur-containing products. Formation of sulfoxide radical cations was unequivocally established by laser flash photolysis experiments showing the absorption bands of 3-CN-NMQ? (λmax = 390 nm) and of the radical cations (λmax = 500-620 nm). The decay rate constants of radical cations, determined by LFP experiments, decrease by increasing the electron-donating power of the arylsulfinyl Y substituent and to a smaller extent by increasing the electron-withdrawing power of the benzylic X substituent. A solvent nucleophilic assistance to the C-S bond cleavage has been suggested, supported by the comparison of substituent effects on the same process occurring in aryl tert-butyl sulfoxide radical cations. DFT calculations, performed to determine the bond dissociation free energy in the radical cations, the transition state energies associated with the unimolecular C-S bond cleavage, and the charge and spin delocalized on their structures, were also useful to endorse the nucleophilic assistance to the C-S scission.
- Del Giacco, Tiziana,Lanzalunga, Osvaldo,Lapi, Andrea,Mazzonna, Marco,Mencarelli, Paolo
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p. 2310 - 2318
(2015/09/08)
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- A comparative study of Cu(II)-assisted vs Cu(II)-free chalcogenation on benzyl and 2°/3°-cycloalkyl moieties
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A relative synthetic strategy toward intermolecular oxidative C -Chalcogen bond formation of alkanes has been illustrated using both Cu(II) assisted vs Cu(II) free conditions. This led to construction of a comparative study of hydrocarbon benzylic and 2°/ 3°-cycloalkyl moieties bond sulfenylation and selenation protocol by the chalcogen sources, particularly sulfur and selenium, respectively. In addition, this protocol disclosed the auspicious formation of sp3 C-S coupling products over leading the sp3 C-N coupling products by using 2-mercaptobenzothiazole (MBT) substrates.
- Sahoo, Santosh K
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p. 2151 - 2157
(2016/01/12)
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- One-pot palladium-catalyzed borrowing hydrogen synthesis of thioethers
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Palladium on magnesium oxide is able to allow a one-pot reaction to synthesize thioethers from thiols and aldehydes formed in situ from the respective alcohol by means of a borrowing hydrogen method. The reaction is initiated by dehydrogenation of the alcohol to give a palladium hydride intermediate and an aldehyde. The latter reacts with a thiol involving most probably the intermediacy of a thionium ion RCHi£S+R, which can be reduced in situ by the metal hydride to afford thioethers. Lending support: Palladium nanoparticles on MgO catalyze the synthesis of thioethers from thiols and aldehydes formed in situ from alcohols by means of the borrowing hydrogen method (see scheme). Dehydrogenation of the alcohol gives a palladium hydride intermediate and an aldehyde. The latter reacts with a thiol through a thionium ion, which is reduced by the metal hydride to afford thioethers.
- Corma, Avelino,Navas, Javier,Rodenas, Tania,Sabater, Maria J.
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p. 17464 - 17471
(2014/01/06)
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- Zn in ionic liquid: An efficient reaction media for the synthesis of diorganyl chalcogenides and chalcogenoesters
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A straightforward and efficient methodology is described to synthesize structurally diverse diorganyl selenides, sulfides, seleno- and thioesters by using commercially available Zn dust in ionic liquid. Excellent yields were achieved under neutral conditions at room temperature in a short time. The solvent/ionic liquid is reusable and exhibited higher performance as compared with organic solvents.
- Narayanaperumal, Senthil,Alberto, Eduardo E.,Gul, Kashif,Kawasoko, Cristiane Yuriko,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
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experimental part
p. 4723 - 4730
(2011/06/27)
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- Bimetallic system for the synthesis of diorganyl selenides and sulfides, chiral β-seleno amines, and seleno- and thioesters
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The bimetallic reagent Sn(II)/Cu(II) in [bmim]BF4 was efficiently used for the cleavage of diaryl diselenides and disulfides and reacts with a variety of organic substrates, such as organic halides, acid chlorides, and β-amino mesylates affording the diorganyl selenides and sulfides within very short reaction times, under mild conditions and with excellent yields, using BMIM-BF4 as a reusable solvent.
- Gul, Kashif,Narayanaperumal, Senthil,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
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supporting information; experimental part
p. 3592 - 3596
(2011/07/31)
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- Silica nanoparticles as a reusable catalyst: A straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts under neutral reaction conditions
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A simple and straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts has been demonstrated using silica nanoparticles (NPs) as a reusable catalyst via the 1,2-addition of thiols to alkenes, alkynes and alkyl/acyl halides, and the 1,4-addition of thiols to conjugated alkenes at room temperature.
- Banerjee, Subhash,Das, Jayanta,Alvarez, Richard P.,Santra, Swadeshmukul
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experimental part
p. 302 - 306
(2010/06/13)
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- Exploring chromium(III)-alkyl bond homolysis with CpCr[(ArNCMe) 2CH](R) complexes
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A range of paramagnetic Cr(III) monohydrocarbyl complexes CpCr[(ArNCMe)2CH](R) (Ar = ortho-disubstituted aryl; R = primary alkyl, trimethylsilylmethyl, benzyl, phenyl, alkenyl, or alkynyl) were synthesized to investigate how varying the steric and electronic properties of the R group affected their propensity for Cr-R bond homolysis. Most complexes were prepared by salt metathesis of known CpCr[(ArNCMe)2CH](Cl) compounds in Et2O with commercial RMgCl solutions, although more sterically demanding combinations of Ar and R groups necessitated the use of halide-free MgR2 reagents and the Cr(III) tosylate or triflate derivatives. Alternative synthetic routes to Cr(III)-R species using the previously reported Cr(II) compounds CpCr[(ArNCMe)2CH] and sources of R? radicals (e.g., BEt3 and air) were also explored. The UV-vis spectra of the CpCr[(ArNCMe)2CH](R) complexes possessed two strong bands with maximum absorbances in the ranges 395-436 nm and 535-582 nm, with the band in the latter range being particularly characteristic of the Cr(III)-R compounds. The Cr-CH2R bond lengths as determined by single-crystal X-ray diffraction were longer than those in the corresponding Cr-CH3 complexes, typically falling in the range 2.10 to 2.13 A. The Cr(III) benzyl compounds displayed longer Cr-CH2Ph distances, while the bond lengths for the alkenyl and alkynyl species were substantially shorter. The rate of Cr-R bond homolysis at room temperature was determined by monitoring the reaction of Cr(III) neopentyl, benzyl, and isobutyl complexes with excess PhSSPh using UV-vis spectroscopy. Although the other primary alkyl, phenyl, and alkenyl compounds did not undergo appreciable homolysis under these conditions, they were cleanly converted to CpCr[(ArNCMe)2CH](SPh) by photolysis.
- MacLeod, K. Cory,Conway, Julia L.,Patrick, Brian O.,Smith, Kevin M.
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supporting information; experimental part
p. 17325 - 17334
(2011/03/01)
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- A novel approach to the practical synthesis of sulfides: An InBr 3-Et3SiH catalytic system promoted the direct reductive sulfidation of acetais with disulfides
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We have demonstrated a facile and direct synthesis of sulfide derivatives using acetais and ketals, derived, from aromatic/ conjugated, aldehydes and aromatic ketones, with disulfides and the InBr3-Et3SiH reducing system., We also succeeded in developing an unprecedented one-pot preparation of an aliphatic sulfide from a disulfide and an aliphatic acetal. (Wiley-VCH Verlag GmbH & Co. KGaA.
- Sakai, Norio,Moritaka, Kohei,Konakahara, Takeo
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supporting information; experimental part
p. 4123 - 4127
(2009/12/09)
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- Mild and efficient deoxygenation of sulfoxides to sulfides with triflic anhydride/potassium iodide reagent system
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It was found that the combination of triflic anhydride/potassium iodide was an effective promoter for the deoxygenation of sulfoxides and gave the corresponding sulfides in excellent yield in acetonitrile at room temperature. It is worth mentioning that this reagent system is chemoselective and tolerates various functional groups, such as alkene, ketone, ester, aldehyde, acid, and oxime. Georg Thieme Verlag Stuttgart.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Karimi, Ahmad
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experimental part
p. 2543 - 2546
(2009/04/04)
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- The syntheses of sulfides by deoxygenation of sulfoxides using Woollins' reagent
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Woollins' reagent (WR) acts as a deoxygenation reagent for a wide range of sulfoxides affording the corresponding sulfides in good to excellent yields (up to 99% isolated yield) under mild conditions.
- Hua, Guoxiong,Woollins, J. Derek
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p. 3677 - 3679
(2008/02/03)
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- A novel method for the deoxygenation of sulfoxides with the PPh 3/Br2/CuBr system
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It was found that the combination of PPh3/Br2/CuBr was an effective promoter for the deoxygenation of sulfoxides and gave the corresponding sulfides in excellent yield in acetonitrile under refluxing conditions. It is worth mentioning that this reagent system is chemoselective, tolerating various functional groups such as carbon-carbon double bond and ketone. Copyright
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Khedri, Mohammad
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p. 1324 - 1325
(2008/03/18)
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- Co-C bond cleavage in the reactions of alkyl, benzyl and heteroaromaticmethyl cobaloximes with arene sulfenyl chloride: Homolytic and heterolytic pathways
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The reactions of arene sulfenyl chlorides, ArSCl, (Ar=Ph, C6Cl5, 2,4 (NO2)2C6H3) with organocobaloximes, RCo(dmgH)2Py, (R=alkyl, benzyl and heteroaromaticmethyl) were carried out under thermal and photochemical conditions. A variety of organic and organometallic products are formed depending upon the substrate cobaloxime. For 3-methoxybenzyl and heteroaromaticmethyl cobaloximes the results suggest that they represent a unique class of cobaloximes whereby both the aromatic ring as well as the Co-C bond are highly activated towards attack by the arene sulfenyl chloride. Both homolytic as well as heterolytic pathways are operative.
- Gupta,Dixit, Vandana,Das, Indira
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- REACTIVITY OF 3,6-DIMETHOXY-3,6-DIMETHYLCYCLOHEXA-1,4-DIENE: NUCLEAR VERSUS BENZYLIC NUCLEOPHILIC SUBSTITUTION
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The treatment of cis/trans-3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (ca. 1/1 mixture; easily prepared electrochemically in multigram scale from p-xylene) under acidic conditions (acetic, trifluoroacetic, sulfuric, or a Lewis acid) yields almost exclusively 2-methoxy-1,4-dimethylbenzene 4, through a trasposition reaction.The use of aqueous hydrochloric or hydrofluoric acid gives 2,5-dimethylphenol 12, and with hydrogen chloride a mixture of 2- and α-chloro-p-xylene (13, 14) is isolated.Different oxygen-, nitrogen-, and sulfur-containing nucleophiles (alcohols,thiols, or hydrazoic acid) react with 3 under acid catalysis giving the corresponding products resulting from a nuclear or/ and benzylic substitution on p-xylene (15 - 20).The reaction of compound 3 with organolithium reagents affords exclusively benzylic products 21 in a regiospecific manner.In all cases the mixtures of isomers are separated by column chromatography.The lithiation of compound 3 with lithium powder or lithium naphthalenide fails, giving p-xylene.A probable mechanism is proposed for the studied reactions.
- Alonso, Francisco,Barba, Isidoro,Yus, Miguel
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p. 2069 - 2080
(2007/10/02)
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- DIRECT CONVERSION OF CARBOXYLIC ACIDS AND CARBOXYLIC ESTERS INTO S,S'-DIPHENYL ACETALS AND PHENYL SULFIDES WITH THEXYLPHENYLTHIOBORANE
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Reaction of carboxylic acids with thexylphenylthioborane in methylene chloride at room temperature gives S,S-diphenyl acetals in high yields and carboxylic esters are converted into phenyl sulfides in the presence of zinc iodide under similar conditions.
- Kim, Sunggak,Kim, Sung Soo
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p. 1913 - 1916
(2007/10/02)
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- The Mechanism of the Reaction of (Arylthio)trimethylgermanes with Benzyl Bromides Giving Aryl Benzyl Sulfides. A Kinetic Study
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A kinetic study has been conducted on the reaction of (arylthio)trimethylgermanes with benzyl bromides.The reaction was found to be second order and the rate was largely accelerated in polar solvents.Both ρ values due to substituents on arylthio and benzyl groups revealed nucleophilic attack of the sulfur atom on benzylic carbon atom as the reaction mechanism.Rates of the reactions of trimethyl(p-tolylthio)stannane with substituted benzyl chlorides were also examined to compare the substituent effects.Steric crowd around the sulfur atom has been found as an important factor to control the reaction mechanism.
- Kozuka, Seizi,Tamura, Shoji,Ishibashi, Satoshi,Ohya, Sadamu,Tagaki, Waichiro
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p. 4061 - 4066
(2007/10/02)
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- Nucleophilic Substitution on 4-Methylbenzyl Thiocyanate with Nucleophiles
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The reactions of 4-methylbenzyl thiocyanate (1) with several nucleophiles have been investigated.Compound 1 possesses three electrophilic sites, i.e., benzylic carbon, sulfur and cyano carbon, to receive nucleophilic attack.PhS- and CN- which have HOMO's of high energy levels appear to attack preferentially the sulfur atom.MeO- was found to attack preferably the cyanide carbon, while amines which have HOMO's of low energy levels prefer benzylic carbon to attack.The nucleophilic substitution on the sulfur or the cyanide carbon generates CN- or p-xylene-α-thiolate anion, strong nucleophiles, as the primary products, which then initiate the complex secondary reactions.The selective reactivities of three attacking sites for nucleophiles in 1 have been rationalized in terms of MO theory.
- Oae, Shigeru,Yamada, Norihiro,Fujimori, Ken,Kikuchi, Osamu
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p. 248 - 256
(2007/10/02)
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- Isotope effects in nucleophilic substitution reactions. IV. The effect of changing a substituent at the α carbon on the structure os SN2 transition states
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Kinetic studies, secondary α-deuterium kinetic isotope effects, primary chlorine kinetic isotope effects (1), Hammett ρ values determined by changing the substituent in the nucleophile, and activation parameters have been used to determine the detailed (relative) structures of the transition states for the S2 reactions between para-substituted benzyl chlorides and thiophenoxide ion.A rationale for the U-shaped Hammett ρ plots observed when para-substituted benzyl compounds react with negatively charged nucleophiles is also presented.
- Westaway, Kenneth Charles,Waszczylo, Zbigniew
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p. 2500 - 2520
(2007/10/02)
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