- Transition-metal-free decarboxylative thiolation of stable aliphatic carboxylates
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A transition-metal-free decarboxylative thiolation protocol is reported in which primary, secondary, tertiary (hetero)aryl acetates and α-CN substituted acetates undergo the decarboxylative thiolation smoothly, to deliver a variety of functionalized aryl alkyl sulfides in moderate to excellent yields. Aryl diselenides are also amenable substrates for construction of C-Se bonds under the simple and mild reaction conditions. Moreover, the protocol is successfully applied to the late-stage modification of pharmaceutical carboxylates with satisfactory chemoselectivity and functional-group compatibility. This journal is
- Xing, Wei-Long,Liu, De-Guang,Fu, Ming-Chen
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p. 4593 - 4597
(2021/02/03)
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- Rhodium-catalyzed Sommelet-Hauser type rearrangement of α-diazoimines: Synthesis of functionalized enamides
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An efficient rhodium catalyzed Sommelet-Hauser type rearrangement of sulfur ylides derived from α-thioesters and N-sulfonyl-1,2,3-triazoles has been successfully accomplished for the synthesis of various functionalized enamides. The developed reaction involves the unprecedented [2,3]-sigmatropic rearrangement of sulfur ylides with the imine motif. Importantly, the method works well with various substituted α-thioesters/-amides/-ketones and substituted N-sulfonyl-1,2,3-triazoles and allows the synthesis of diverse enamide derivatives in good to excellent yields. The reaction was also successfully extended to the one-pot synthesis of enamides from terminal alkynes.
- Anbarasan, Pazhamalai,Ramachandran, Kuppan,Reddy, Angula Chandra Shekar,Reddy, Palagulla Maheswar
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supporting information
p. 5649 - 5652
(2020/06/09)
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- Sulfoxide Reduction/C(sp3)-S Metathesis Cascade in Ionic Liquid
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A sulfoxide reduction/C-S bond metathesis cascade between sulfoxides and alkyl bromides has been developed to access high-value sulfides without the use of any catalysts or bases. In this cascade, classical Kornblum oxidation is employed to reduce sulfoxides with alkyl bromides in ionic liquid. This protocol features high functional tolerance, mild conditions, promising scalability, and sustainable solvents.
- Liu, Chenjing,Chen, Dengfeng,Fu, Yuanyuan,Wang, Fei,Luo, Jinyue,Huang, Shenlin
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supporting information
p. 5701 - 5705
(2020/07/24)
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- Compound, preparation method thereof, medical intermediate and application thereof
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The invention relates to the technical field of chemical synthesis, and particularly discloses a compound, a preparation method thereof, a medical intermediate and an application thereof, the compoundcomprises the following raw materials: thioether, bromide and a proper amount of organic solvent, and the molar weight ratio of thioether to bromide is 1: (2-8). According to the compound provided bythe invention, thioether, bromide and a proper amount of organic solvent are used as raw materials, and the thioether compound can be obtained without adopting a catalyst, so that the problems of metal residues and the like are fundamentally eliminated, the provided preparation method is simple to operate, the method is simple in process and high in yield, the thioether compound is prepared through thioether metathesis reaction, metal catalysis is not needed in the whole reaction, meanwhile, the reaction condition is mild, the substrate range is wide, the problem of metal pollution existing in an existing thioether compound synthesis method is solved, and the method has wide market prospects in the fields of organic synthesis, medicine synthesis and the like.
- -
-
Paragraph 0060-0067
(2020/08/06)
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- Rhodium-Catalyzed Rearrangement of S/Se-Ylides for the Synthesis of Substituted Vinylogous Carbonates
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An efficient rhodium-catalyzed unprecedented oxa-[2,3]-sigmatropic rearrangement of sulfur ylide derived from α-thioesters/ketones and diazo carbonyl compounds has been accomplished for the synthesis of various sulfur-tethered vinylogous carbonates in good to excellent yields. Important features of the developed reaction include wide functional group tolerance, excellent chemo- and regioselectivity, and efficient rearrangement involving the carbonyl motif. The present reaction also equally works well with α-selenoesters for the synthesis of seleno-containing vinylogous carbonates.
- Reddy, Angula Chandra Shekar,Anbarasan, Pazhamalai
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supporting information
p. 9965 - 9969
(2019/12/24)
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- Dealkylative intercepted rearrangement reactions of sulfur ylides
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Sulfur ylides are well-known to undergo sigmatropic rearrangement reaction. Herein, we describe a novel reactivity of sulfur ylides, which provides access to the product of a formal functional group metathesis upon dealkylative interception of the rearrangement process. Using a simple iron catalyst and in situ generated diazoalkanes this method provides access to α-mercaptoacetonitrile derivatives.
- Empel, Claire,Hock, Katharina J.,Koenigs, Rene M.
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supporting information
p. 338 - 341
(2019/01/09)
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- Iron-catalysed carbene-transfer reactions of diazo acetonitrile
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A continuous-flow protocol for the synthesis of diazo acetonitrile was developed. It was further applied in iron-catalysed insertion reactions of diazo acetonitrile into N-H and S-H bonds to yield valuable α-substituted acetonitrile, including gram-scale synthesis.
- Empel, Claire,Hock, Katharina J.,Koenigs, Rene M.
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supporting information
p. 7129 - 7133
(2018/10/24)
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- Aryl sulfoxide, thioether compound, synthesis method and application thereof
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The invention discloses a method for selective synthesis of an aryl sulfoxide compound (III) and an aryl thioether compound (IV). According to the invention, in a reactive solvent, an aryl high iodinesalt is adopted as the reaction raw material, aryl/alkyl thiosulfate is taken as the vulcanizing reagent, under the catalysis of visible light and a photosensitive reagent, and under the action of lewis acid and alkali, when the reaction atmosphere is nitrogen, the thioether compound (IV) can be generated, and when the reaction atmosphere is air, the sulfoxide compound (III) can be generated. Thesynthesis method provided by the invention has the advantages of easily available and cheap raw materials, simple reaction operation, mild and environment-friendly reaction conditions, high yield, and excellent functional group tolerance. The invention also discloses the new aryl sulfoxide compound (III) and aryl thioether compound (IV), also successfully realizes later modification of drugs andsugar, and realizes the formal synthesis of some drugs, and provides an efficient method for selective construction of thioether and sulfoxide compounds.
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Paragraph 0197-0200
(2018/04/21)
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- Inhibitors of the Diadenosine Tetraphosphate Phosphorylase Rv2613c of Mycobacterium tuberculosis
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The intracellular concentration of diadenosine tetraphospate (Ap4A) increases upon exposure to stress conditions. Despite being discovered over 50 years ago, the cellular functions of Ap4A are still enigmatic. If and how the varied Ap4A is a signal and involved in the signaling pathways leading to an appropriate cellular response remain to be discovered. Because the turnover of Ap4A by Ap4A cleaving enzymes is rapid, small molecule inhibitors for these enzymes would provide tools for the more detailed study of the role of Ap4A. Here, we describe the development of a high-throughput screening assay based on a fluorogenic Ap4A substrate for the identification and optimization of small molecule inhibitors for Ap4A cleaving enzymes. As proof-of-concept we screened a library of over 42, 000 compounds toward their inhibitory activity against the Ap4A phosphorylase (Rv2613c) of Mycobacterium tuberculosis (Mtb). A sulfanylacrylonitril derivative with an IC50 of 260 ± 50 nM in vitro was identified. Multiple derivatives were synthesized to further optimize their properties with respect to their in vitro IC50 values and their cytotoxicity against human cells (HeLa). In addition, we selected two hits to study their antimycobacterial activity against virulent Mtb to show that they might be candidates for further development of antimycobacterial agents against multidrug-resistant Mtb.
- G?tz, Kathrin H.,Hacker, Stephan M.,Mayer, Daniel,Dürig, Jan-Niklas,Stenger, Steffen,Marx, Andreas
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p. 2682 - 2689
(2017/10/27)
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- Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis
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Sulfoxides and sulfides are two important functional groups in organic molecules, containing different valence states of sulfur. Both sulfoxidation and sulfenylation with common sulfurating reagents were successfully tuned via a facile variation of the atmosphere under photocatalyzed conditions. The sulfoxidation and sulfenylation transformations involved tandem electron-/energy-transfer and single-electron-transfer processes, respectively. Late-stage sulfoxidation for pharmaceuticals and sugar derivatives was established to be highly compatible. Divergent formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuticals were switchably implemented. Gram-scale operations further demonstrated the practicability of the protocol.
- Li, Yiming,Wang, Ming,Jiang, Xuefeng
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p. 7587 - 7592
(2017/11/10)
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- Cs2CO3-promoted carbon–sulfur bond construction via cross dehydrogenative coupling of thiophenols with acetonitrile
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A novel protocol for the construction of carbon–sulfur bonds has been achieved via halogen-free Cs2CO3-promoted cross dehydrogenative coupling (CDC) of thiophenols with acetonitrile. This transformation provides a straightforward route to the synthesis of sulfenylated acetonitriles in up to 80% yield.
- Chen, Qian,Huang, Yulin,Wang, Xiaofeng,Wen, Chunxiao,Yan, Xinxing,Zeng, Jiekun
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supporting information
p. 3928 - 3931
(2017/09/21)
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- Synthesis of nitriles from amines using nanoscale Co3O4-based catalysts via sustainable aerobic oxidation
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The selective oxidation of amines for the benign synthesis of nitriles under mild conditions is described. Key to success for this transformation is the application of reusable cobalt oxide-based nanocatalysts. The resulting nitriles constitute key precursors and central intermediates in organic synthesis.
- Natte, Kishore,Jagadeesh, Rajenahally V.,Sharif, Muhammad,Neumann, Helfried,Beller, Matthias
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supporting information
p. 3356 - 3359
(2016/04/09)
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- A practical and chemoselective Mo-catalysed sulfoxide reduction protocol using a 3-mercaptopropyl-functionalized silica gel (MPS)
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A convenient sulfoxide deoxygenation procedure using a mercaptopropyl-functionalized silica gel as the reducing agent is described. This new protocol based on a heterogeneous reagent displays broad scope and tolerance to reducible functional groups and, from an experimental point of view, enhances previous methods by simplifying the isolation of the sulfide to a simple filtration.
- García, Nuria,Fernández-Rodríguez, Manuel A.,García-García, Patricia,Pedrosa, María R.,Arnáiz, Francisco J.,Sanz, Roberto
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p. 27083 - 27086
(2016/03/25)
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- "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2O3)-based catalysts applying molecular oxygen.
- Jagadeesh, Rajenahally V.,Junge, Henrik,Beller, Matthias
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- Exploitation of dual character of CN moiety in the synthesis of uniquely decorated 3 H-pyrroles: A rare observation
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This is the first report of an innovative, one-pot, organocatalyzed, multicomponent synthesis of 3H-pyrroles from ketones, thiols, and malononitrile in ecofriendly solvent water. The approach to 3H-pyrroles presented herein offers, for the first time, an unprecedented coupling which leads to the construction of the nitrogen containing ring without starting from any amine moiety. In this context, cyanide-based multicomponent reactions involving the dual nature of the CN moiety has blossomed in an unprecedented way.
- Das, Paramita,Ray, Suman,Mukhopadhyay, Chhanda
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supporting information
p. 5622 - 5625
(2013/12/04)
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- Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage
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Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright
- Shen, Tao,Wang, Teng,Qin, Chong,Jiao, Ning
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supporting information
p. 6677 - 6680
(2013/07/25)
-
- Pinacol as a new green reducing agent: Molybdenum-catalyzed chemoselective reduction of sulfoxides and nitroaromatics
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Pinacol is disclosed as a new chemoselective and environmentally benign reducing agent for sulfoxides and nitroaromatics assisted by readily available dichlorodioxomolybdenum(VI) complexes as catalysts. A wide range of substrates including those bearing challenging functional groups has been efficiently and selectively reduced with acetone and water being the only by-products of these reactions. Copyright
- Garcia, Nuria,Garcia-Garcia, Patricia,Fernandez-Rodriguez, Manuel A.,Rubio, Ruben,Pedrosa, Maria R.,Arnaiz, Francisco J.,Sanz, Roberto
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supporting information; experimental part
p. 321 - 327
(2012/04/11)
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- Highly efficient gold nanoparticle catalyzed deoxygenation of amides, sulfoxides, and pyridine N-oxides
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Selective deoxygenation is one of the most important reactions in the areas of total synthesis, biological chemistry, and transformation of renewable biomass resources.To date, many useful methods for the selective deoxygenation of oxygen-containing organic molecules, such as amides, nitro compounds, epoxides, sulfoxides, and those with Noxide groups, have been developed. However, these methods often include stoichiometric reactions. Some successful catalysts have been reported,but most of them are homogeneous systems and still suffer from low activities and selectivities, harsh reaction conditions, and tedious workup procedures. Therefore, further development of highly efficient heterogeneous catalysts for selective deoxygenations is highly desired.
- Mikami, Yusuke,Noujima, Akifumi,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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experimental part
p. 1768 - 1772
(2011/03/21)
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- Catalytic enantioselective mannich-type reaction with β-phenyl sulfonyl acetonitrile
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Figure presented The organocatalytic addition of β-phenyl sulfonyl acetonitrile 1 to either N-Boc-protected α-amido sulfones or imines allowed the synthesis of enantioenriched α-unsubstituted β-amino nitriles through a Mannich-type reaction.
- Gonzalez, Pedro B.,Lopez, Rosa,Palomo, Claudio
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supporting information; experimental part
p. 3920 - 3922
(2010/08/06)
-
- 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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scheme or table
p. 17325 - 17334
(2011/03/01)
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- Efficient synthesis of unsymmetrical disulfides through sulfenic acids
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Unsymmetrical disulfides, some of which are biologically interesting, were prepared by the in situ generation of sulfenic acids from suitable sulfinyl precursors and their coupling with various thiols. This methodology represents an efficient and mild procedure to obtain disulfides in excellent yields. It allows the presence of base/acid and/or thermolabile functional groups in both the sulfenic acid and the thiol on the basis of the choice of suitable sulfenic acid precursors and offers wide chances of modulating the construction of the disulfide bridge between different structural skeletons such as homo- and heteroaromatic, amino acidic and sugar residues. Wiley-VCH Verlag GmbH & Co. KGaA.
- Aversa, Maria Chiara,Barattucci, Anna,Bonaccorsi, Paola
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scheme or table
p. 6355 - 6359
(2011/03/19)
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- Synthesis of organic sulfides via Zn/AlCl3 system in aqueous media
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An efficient procedure for preparation of various sulfides has been introduced through a simple reaction of disulfides with suitable alkyl or aryl halides which is promoted by commercial zinc powder in the presence of AlCl3 in aqueous media at 65°C.
- Lakouraj,Movassagh,Fadaei
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p. 1237 - 1242
(2007/10/03)
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- Synthesis of phenylthiomethyl compounds from trichloromethyl derivatives
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A new method for the conversion of trichloromethyl compounds into the corresponding phenylthiomethyl derivatives by reaction with sodium thiophenolate in the presence of thiophenol is described. This transformation proceeds at room temperature in high yield and has been applied to a variety of trichloromethyl compounds.
- Romero-Ortega, Moises,Fuentes, Aydee,Gonzalez, Carlos,Morales, David,Cruz, Raymundo
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p. 225 - 227
(2007/10/03)
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- Magnesium methoxide complexation in the control of chemical reactions
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The insolubility of complex magnesium chelates makes experimentation difficult, so smaller complexes are used as models for NMR and deuteration studies.Treatment of methyl cyanoacetate with magnesium methoxide however does not give a simple chelate but a novel kinetic Claisen condensation product, methyl 2,4-dicyano-3-hydroxybut-2-enoate, sequestrated as its magnesium-derivative.Replacement of magnesium methoxide by the non-chelating base sodium methoxide gives the known thermodynamic 1,2-addition product, dimethyl 3-amino-2-cyanopent-2-enedioate.A crossed Claisen product, dimethyl 2-cyano-3-hydroxybut-2-enedioate, has been obtained from diethyl oxalate and methyl cyanoacetate in the presence of magnesium methoxide.However, replacement of the oxalate by phenyl cyanomethyl sulfoxide gives a crossed 1,2-addition product, methyl 3-amino-2-cyano-4-phenylsulfinylbut-2-enoate.Reactions between phenyl cyanomethyl sulfoxide or phenylsulfinylacetone and methyl 2-methoxymethyleneacetoacetate are carried out in the presence of varying amounts of sodium and magnesium methoxides.The products are pyrones, pyridones and aminobenzoates.When sodium methoxide is used in the phenylsulfinylacetone reaction the major product is a pyridine, but with magnesium methoxide it is a hydroxyaminobenzoate.This dichotomy may be explained as a consequence of magnesium complexation by the substrate.
- Baker, S. Richard,Cadman, Michael L. F.,Crombie, Leslie,Edwards, David A. V.,Mistry, Jayshree
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p. 2705 - 2714
(2007/10/03)
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- Relationships between conformational behaviour and binding affinity towards β1 and β2 adrenoceptors of some chiral phenoxypropanolamines with bulky N-substituents
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The optical isomers of a series of phenoxypropanolamine compounds with N-substituents bulkier than isopropyl have been synthesized, and their binding affinity towards β1 and β2-adrenoceptors has been determined. A computational study, including a Molecular Dynamics (MD) simulation and quenching in water and a GRID analysis provided some useful suggestions for possible interpretation patterns for the different affinity exhibited by the compounds studied.
- Villa,Villa,Pallavicini,Romeo,Valoti,Ferri,Iuliano,Brunello
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p. 643 - 658
(2007/10/03)
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- Alkadiene derivatives, their preparation, and pharmaceutical compositions containing them
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Substituted alkadienes of the formula: STR1 in which R1 is hydroxy or acetoxy, R2 is hydrogen, carboxy, alkoxycarbonyl, phenyl or benzoyl, and R3 is alkylthio or alkoxy and R4 is naphthoyl or optionally substituted benzoyl, or R3 is alkoxycarbonyl, cycloalkyloxycarbonyl or cyano and R4 is alkyl, naphthyl, optionally substituted phenyl, alkylthio, naphthylmethanethio, optionally substituted benzylthio, optionally substituted phenylthio, naphthylthio, phenethylthio or allylthio, or R3 and R4 form, with the carbon atom to which they are attached, a ring-system of formula: STR2 in which R5 is hydrogen or alkoxy and X is methylene or S inhibit 5-lipoxygenase and are useful, for example, as anti-inflammatories.
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- Rearrangements of 2-Phenylthioethanols with Alkenyl, Alkynyl, Ester, and Other Functionalised Alkyl Substituents at the Migration Origin: Synthesis of γ-Phenylthiocrotonate Esters
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The effects of functional groups near the migration origin in and PhS shifts are explored: an α-CO2R group prevents migration, α or β vinyl groups have only steric effects, alkynyl or CO2Et groups encourage rearrangement and provide routes to γ-phenylthio unsaturated esters and ketones.
- Brownbridge, Peter,Hunt, Paul G.,Warren, Stuart
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p. 1695 - 1706
(2007/10/02)
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- Intramolecular Stereospecific Pummerer Reactions of Aryl (Substituted-methyl) Sulfoxides Bearing Electron-withdrawing Groups with Acetic Anhydride
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The Pummerer reaction of optically active cyanomethyl aryl sulfoxides with acetic anhydride gave the corresponding α-acetoxy sulfides which were induced with a partial asymmetry nearly 30percent at α-carbon, while the 18O-label of the original sulfoxides was retained in more than 85percent in the resulting ester, the Pummerer reaction product.Kinetic experiments with cyanomethyl (p-substituted phenyl) sulfoxides and α,α-dideuterated cyanomethyl p-tolyl sulfoxide in the reaction with acetic anhydride containing a small amount of acetic acid revealed that the rates were correlated with Hammett ?-values and ρ-value of -0.70 was obtained, while the kinetic isotope effect was practically nil, i.e., kH/kD=1.01.These observations indicate clearly that the rearrangement is intramolecular and proceeds via forming a very intimate ion-pair and the rate-determining step is believed to be the S-O bond cleavage after the initial reversible acylation and deprotonation.Elimination of acetic acid proceeds through the Eleb type process.The uneven distribution of 18O in the two oxygens of the resulted ester, i.e., ether and carbonyl oxygens, suggests the recombination of the α-sulfenyl carbonium ion and acetate ion to be very rapid.The pummerer reaction of optically active N,N-dimethyl-p-tolyl-sulfinylacetamide with excess acetic anhydride also gave the corresponding α-acetoxy sulfide in optically active form.In the presence of di-cyclohexylcarbodiimide (DCC), the Pummerer reaction was found to be highly stereoselective affording the corresponding α-acetoxy sulfide with 65percent e.e.Other optically active α-carbonyl-substituted alkyl sulfoxides, i.e., ethyl p-tolylsulfinylacetate and ω-(p-tolylsulfinyl)acetophenone also gave the corresponding highly optically active Pummerer rearrangement products in the treatment with acetic anhydride/DCC system.The Pummerer reaction of the 18O-labeled sulfoxides with acetic anhydride/DCC system gave the corresponding α-acetoxy sulfides which retained much of the original 18O-labels of the sulfoxides.These observations reveal clearly that in the Pummerer reaction of these compounds the acetoxyl migration is intramolecular and takes place through intimate ion-pairs.
- Numata, Tatsuo,Itoh, Osamu,Yoshimura, Toshiaki,Oae, Shigeru
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p. 257 - 265
(2007/10/02)
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- Reaction of Vinyl Sulphone with α-Metallated Nitriles
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Vinyl sulphones (1) were subjected to nucleophilic addition by α-lithionitriles (2) and gave cyclized products, 3-oxothian 1,1-dioxides (3) or cyclopropane derivatives (4), in satisfactory yields according to the substituents on the reagents.The cyclopropanation reactions could be extended to the formation of cyclopropyl sulphides (12) - (16) in good yields.
- Agawa, Toshio,Yoshida, Yasuo,Komatsu, Mitsuo,Ohshiro, Yoshiki
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p. 751 - 755
(2007/10/02)
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- Substitution Reactions of Thallous Thiophenoxide and Thallous Phenylselenide with Halogen-Bearing Substrates
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Thallous thiophenoxide (1) and thallous selenide (2) were prepared by the action of either thallous ethoxide or thallous pentoxide on thiophenol and benzeneselenol.The reagents 1 and 2 reacted readily with aroyl and acyl halides, imidoyl chlorides, α-halo ketones, α-halo esters, α-halo lactones, α-halo carboxylic acids, allyl halides, alkyl halides, chlorotrimethylsilane, chloroacetonitrile, and N-chlorosuccinimide to give substitution products and varying amounts of diphenyl disulfide and diphenyl diselenide.The reactions were run as heterogeneous mixtures in ether.The origin of the diphenyl disulfide and diphenyl diselenide was homolytic cleavage of the thallium-sulfur or thallium-selenium bond, on the basis of the products derived from the reactions of N-chlorosuccinimide with 1 and 2.
- Detty, Michael R.,Wood, Gary P.
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