- Synthesis and reactivity of α-sulfenyl-β-chloroenones, including oxidation and Stille cross-coupling to form chalcone derivatives
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The synthesis of a range of novel α-sulfenyl-β-chloroenones from the corresponding α-sulfenylketones, via a NCS mediated chlorination cascade, is described. The scope of the reaction has been investigated and compounds bearing alkyl- and arylthio substituents have been synthesised. In most instances, the Z α-sulfenyl-β-chloroenones were formed as the major products, while variation of the substituent at the β-carbon position led to an alteration in stereoselectivity. Stille cross-coupling with the Z α-sulfenyl-β-chloroenones led to selective formation of Z sulfenyl chalcones, while the E α-sulfenyl-β-chloroenones did not react under the same conditions. Oxidation of the Z α-sulfenyl-β-chloroenones was followed by isomerisation, leading to the E α-sulfinyl-β-chloroenones. Stille cross-coupling with the E α-sulfinyl-β-chloroenones produced the E sulfinyl chalcones. Either the E or Z sulfinyl chalcones can be obtained by altering the sequence of oxidation and Stille cross-coupling.
- Kearney, Aoife M.,Murphy, Linda,Murphy, Chloe C.,Eccles, Kevin S.,Lawrence, Simon E.,Collins, Stuart G.,Maguire, Anita R.
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supporting information
(2021/05/04)
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- Synthesis of a new series of Ni(II), Cu(II), Co(II) and Pd(II) complexes with an ONS donor Schiff base: Crystal structure, DFT study and catalytic investigation of palladium and nickel complexes towards deacylative sulfenylation of active methylenes and regioselective 3-sulfenylation of indoles: Via thiouronium salt formation
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A series of Ni(ii), Cu(ii), Co(ii), and Pd(ii) complexes have been synthesized with a chelating Schiff base ligand coordinated to a metal center with ONS donor atoms. The ligand and complexes are characterized by elemental analysis and spectroscopic techniques like FT-IR, 1H-NMR, and UV-Visible spectroscopy. The single crystal structure of the Pd(ii) complex is obtained by X-ray diffraction analysis and exhibits slightly distorted square planar geometry. The structure is optimized by DFT, TD-DFT calculation to elaborate the electronic structure and NBO for the charge distribution analysis of the Pd(ii) complex. The synthesized Pd(ii) and Ni(ii) complexes as catalysts have been investigated in the C-S cross-coupling of indoles and active methylenes. The metal propelled regioselective transformation afforded 3-sulfenylated indoles while β-diketones favored deacylated monosulfenyl ketones in an excellent yield via thiouronium salt formation. The Pd(ii) complex displays slightly better reactivity whereas the Ni(ii) complex is cost-efficient. The method is fast, easy to handle and cost effective in terms of high reactivity of catalysts, use of non-toxic solvents, and cheaper aryl halides and thiourea replace conventional sulfur sources, providing a practical access to organic transformations.
- Devi, Namita,Sarma, Kuladip,Rahaman, Rajjakfur,Barman, Pranjit
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p. 4583 - 4595
(2018/04/03)
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- Tandem Pd/Au-catalyzed route to α-sulfenylated carbonyl compounds from terminal propargylic alcohols and thiols
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An efficient and highly atom-economical tandem Pd/Au-catalyzed route to α-sulfenylated carbonyl compounds from terminal propargylic alcohols and thiols has been developed. This one-step procedure has a wide substrate scope with respect to substituents at
- Biswas, Srijit,Watile, Rahul A.,Samec, Joseph S. M.
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supporting information
p. 2159 - 2163
(2014/03/21)
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- Asymmetrische Katalysen, 58. Mitt.: Enantioselektive S-H- und C-H-Insertionen mit optisch aktiven Rh(II)- und Cu(II)-Katalysatoren
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The substrates for the S-H insertion reaction were azibutanone 2 and thiophenol 3.Methyl 2-diazo-3-oxo-heptane-caboxylate 26 was used as the substrate in an intramolecular C-H insertion.Both reactions were carried out enantioselectively in the presence of optically active rhodium(II) and copper(II) catalysts.For the S-H insertion optical inductions up to 13.8percentee and for the C-H insertion up to 14percentee were achieved.
- Brunner, Henri,Wutz, Konrad,Doyle, Michael
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p. 755 - 764
(2007/10/02)
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- Electrophilic Addition of 4'-Nitrobenzenesulphenanilide to Alkynes in Acetic Acid. A Synthesis of β-Acetoxyvinyl Sulphides
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4'-Nitrobenzenesulphenanilide reacts at room temperature with simple alkyl- and aryl-alkynes in acetic acid in the presence of boron trifluoride-diethyl ether to afford products of acetoxysulphenylation in moderate to good yields.The addition products are
- Benati, Luisa,Casarini, Daniele,Montevecchi, Pier Carlo,Spagnolo, Piero
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p. 1113 - 1116
(2007/10/02)
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- A CONVENIENT SYNTHESIS OF Β-KETO PHENYL SULPHIDES FROM ALKYNES.
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β-Keto sulphides can be conveniently prepared by BF3-promoted reaction of 4'-nitrobenzenesulphenanilide in acetonitrile or acetic acid and subsequent hydrolysis of the resulting β-acetamidino- or β-acetoxy-vinyl phenyl sulphides.
- Benati, L.,Montevecchi, P.C.,Spagnolo, P.
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p. 2381 - 2384
(2007/10/02)
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- Replacement of the Activated Nitro Group by a Phenylthio Group
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The nitro group, activated by a carbonyl group, alkoxycarbonyl group or a phenyl group, can be replaced by a phenylthio group in the reaction with benzenethiol or its potassium salt.This reaction proceeds in the electron transfer mechanism, and is applicable to the general syntheses of α-phenylthio ketones, α-phenylthio carboxylic esters and α-phenylthio alkylbenzenes from primary nitro compounds.
- Miyake, Hideyoshi,Yamamura, Kimiaki
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- Synthesis of α-Phenylthio Enones and Esters of α-Phenylthio Alkenoic Acids
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The title compounds can be made by a Pummerer dehydration from the corresponding saturated sulphoxides.The alkylation of anions from saturated and unsaturated ketones is described.
- Durman, John,Grayson, J.Ian,Hunt, Paul G.,Warren, Stuart
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p. 1939 - 1946
(2007/10/02)
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- REGIOSELECTIVE SULFENYLATION OF OXIME DIANIONS. A NOVEL AND USEFUL METHOD FOR THE REGIOSELECTIVE RING CLEAVAGE
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Treatment of the dianions of cyclic ketoximes with diphenyl disulfide underwent a regioselective sulfenylation at the syn α-carbons.Regioselective alkylation of cyclic ketoxime dianions, followed by sulfenylation with diphenyl disulfide, produced α-alkyl-
- Hiroi, Kunio,Otsuka, Masahiko,Sato, Shuko
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p. 1907 - 1910
(2007/10/02)
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- REGIOSPECIFIC SYNTHESIS OF α-(PHENYLTHIO)KETONES VIA RHODIUM(II) ACETATE CATALYSED ADDITION OF THIOPHENOL TO α-DIAZOKETONES
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αα-Addition of thiophenol to α-diazoketones is catalysed efficiently by rhodium(II) acetate in benzene solution at room temperature, offering a convenient regiospecific route to a variety of α-(phenylthio)ketones.
- McKervey, M. Anthony,Ratananukul, Piniti
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p. 2509 - 2512
(2007/10/02)
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- NEW ACETYLENIC MICHAEL RECEPTOR EQUIVALENTS. PART I : SYNTHESIS OF α-SULFENYL - AND α-SULFINYL ACRYLIC DERIVATIVES.
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The synthesis of α-thioarylated β-unsubstituted acrilic derivatives is reported.
- Leyendecker, Francois,Comte, Marie-Therese
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p. 5031 - 5034
(2007/10/02)
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- NUCLEOPHILIC SUBSTITUTION OF α-HALO KETONES. XXI. STRUCTURE-REACTIVITY RELATIONSHIPS IN THE ACETOLYSIS OF 3-SUBSTITUTED 1-CHLORO-3-PHENYLTHIO-2-PROPANONES
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The acetolyses of α-chloro ketones 1a-d have been re-investigated under standard conditions and compared with those of the corresponding isomeric substrates 2a-d.It has been shown that participation by the neighbouring phenylthio group, involving a 1-3 shift of the latter, does occur in part even in the case of 1d, while it is the only process in the case of 1e.A few structure-reactivity relationships in the two series of substrates are discussed.
- Pusino, Alba,Rosnati, Vittorio,Saba, Antonio,Franco, Andrea
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p. 475 - 482
(2007/10/02)
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- REACTION OF 2-ALKOXY-1,3-DIENES WITH ALKYL AND ARYL HYDROSULFIDES
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The reactions of 2-methoxy-, 2-ethoxy-, 2-isopropoxy-, and 2-tert-butoxy-1,3-butadienes with ethyl hydrosulfide and of 2-methoxy-1,3-butadiene with methyl hydrosulfide under the conditions of nucleophilic reaction (sodium, methanol) were investigated.The reactions of 2-methoxy- and 2-ethoxy-1,3-butadienes with phenyl and ethyl hydrosulfides and also of 2-methoxy- and 2-tert-butoxy-1,3-butadienes with methyl hydrosulfide were carried out under radical conditions.During nucleophilic reaction attack by the thiyl radical takes place exclusively at the terminal carbon atom of the unsubstituted double bond in accordance with the distribution of electron density in the molecule of the dienyl ether; a mixture of 2-alkoxy-4-alkyl-thio-2-butene and 2-alkoxy-4-alkylthio-1-butene is formed.In the case of radical addition a mixture of isomers with preferential addition of the thiyl radical at the terminal atom of the α-alkoxyvinyl group is formed, and the 2-alkoxy-1-alkyl(aryl)thio-2-butene formed here isomerizes to 2-alkoxy-1-alkyl(aryl)thio-1-butene.
- Kobesheva, N. I.,Kheruze, Yu. I.,Petrov, A. A.
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p. 1226 - 1232
(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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