- Photochemical Oxidation of Pt(IV)Me3(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates
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We report the formation of dinuclear complexes from, and photochemical oxidation of, (CH3)3-Pt(IV)(N^N) (N^N = 1,2-diimine derivatives) complexes of thiophenolate ligands to the analogous sulfinates (CH3)3Pt(N^N)(SO2Ph) and structural, spectroscopic, and
- Mala, Barbora,Murtagh, Laura E.,Farrow, Charlotte M. A.,Akien, Geoffrey R.,Halcovich, Nathan R.,Allinson, Sarah L.,Platts, James A.,Coogan, Michael P.
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- Green Aerobic Oxidation of Thiols to Disulfides by Flavin-Iodine Coupled Organocatalysis
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Coupled catalysis using a riboflavin-derived organocatalyst and molecular iodine successfully promoted the aerobic oxidation of thiols to disulfides under metal-free mild conditions. The activation of molecular oxygen occurred smoothly at room temperature through the transfer of electrons from the iodine catalyst to the biomimetic flavin catalyst, forming the basis for a green oxidative synthesis of disulfides from thiols.
- Iida, Hiroki,Kozako, Ryo,Oka, Marina
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supporting information
p. 1227 - 1230
(2021/06/21)
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- Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects
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Direct fluorination of ortho-, meta- and para-substituted aromatic thiols and disulfides using elemental fluorine afforded substituted (pentafluorosulfanyl)benzenes. This work thus represents the first study of the scope and limitation of direct fluorination for the synthesis of new SF5-containing building blocks. Fluorinations in batch and flow modes were compared. A comprehensive computational study was carried out employing density functional and wave function methods to elucidate the reaction mechanism of the transformation of ArSF3 into ArSF5. Eliminating various nonradical pathways, it has been shown that the reaction proceeds by a radical mechanism, initiated by the attack of the F. on the ArSF3 moiety, propagated via an almost barrierless F2+ArSF4 .→ArSF5+F. step and terminated by the ArSF4 .+F.→ArSF5. Most of the calculated data are in very good agreement with experimental observations concerning the ortho-substituent effect on the reaction rates and yields.
- Ajenjo, Javier,Klepetá?ová, Blanka,Greenhall, Martin,Bím, Daniel,Culka, Martin,Rulí?ek, Lubomír,Beier, Petr
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supporting information
p. 11375 - 11382
(2019/08/20)
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- Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy-amino-λ6-sulfanenitrile Intermediate
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Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry, and provide attractive bioisosteres for sulfonamides. However, there remain few operationally simple methods for their preparation. Here, the synthesis of NH-sulfonimidamides is achieved directly from sulfenamides, themselves readily formed in one step from amines and disulfides. A highly chemoselective and one-pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source, and in the presence of 1 equivalent of acetic acid. A wide range of functional groups are tolerated under the developed reaction conditions, which also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel S≡N sulfanenitrile species as intermediates. Several alkoxy-amino-λ6-sulfanenitriles are prepared with different alcohols, and shown to be alkylating agents to a range of nucleophiles.
- Briggs, Edward L.,Tota, Arianna,Colella, Marco,Degennaro, Leonardo,Luisi, Renzo,Bull, James A.
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supporting information
p. 14303 - 14310
(2019/09/06)
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- 18F-Fluoroform: A 18F-trifluoromethylating agent for the synthesis of SCF218F-aromatic derivatives
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Herein the synthesis of various SCF218F-containing derivatives is reported by a transition metal-free process. By using HCF218F, readily generated from a bench-stable difluoromethyl sulfonium salt, various aromatic disulfides were easily converted into the desired radiolabelled trifluoromethylthiolated compounds in the presence of a base. This protocol allowed the formation of the SCF218F-containing aromatic derivatives in good to excellent radiochemical yields. This process was also extended to the corresponding selenium derivative.
- Carbonnel, Elodie,Besset, Tatiana,Poisson, Thomas,Labar, Daniel,Pannecoucke, Xavier,Jubault, Philippe
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supporting information
p. 5706 - 5709
(2017/07/10)
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- Shedding light on an ultra-bright photoluminescent lamellar gold thiolate coordination polymer [Au(: P -SPhCO2Me)]n
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The first structure elucidation of a lamellar gold thiolate coordination polymer is described. [Au(p-SPhCO2Me)]n is obtained from the simultaneous esterification of mercaptobenzoic acid and reduction of the Au(iii) precursor. Despite the presence of aurophilic interactions, the intense phosphorescence (QY ~ 70%) originates from intra-ligand and metal-to-ligand transitions.
- Lavenn, Christophe,Guillou, Nathalie,Monge, Miguel,Podbev?ek, Darjan,Ledoux, Gilles,Fateeva, Alexandra,Demessence, Aude
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supporting information
p. 9063 - 9066
(2016/07/21)
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- Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide
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A tunable and practical synthesis of electrophilic sulfenylating reagents, thiosulfonates and disulfides, from inexpensive and easily available sulfonyl chlorides, has been developed. By appropriate choice of solvents, the reaction of sulfonyl chlorides and tetrabutylammonium iodide gave the target products in good to excellent yields, respectively. These transformations probably proceed through a reducing–coupling pathway. (Figure presented.).
- Zheng, Yong,Qing, Feng-Ling,Huang, Yangen,Xu, Xiu-Hua
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supporting information
p. 3477 - 3481
(2016/11/13)
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- Haloacid/dimethyl sulfoxide-catalyzed synthesis of symmetrical disulfides by oxidation of thiols
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A novel method is developed for the oxidation of thiols to the corresponding disulfides using 20 mol % haloacid (HBr or HI) in combination with dimethyl sulfoxide. A tentative mechanism is proposed for the oxidation. In addition to the advantages of cost-effectiveness, simple processes, and broad functional group tolerance, the exclusive formation of disulfides is the principle reward of this methodology while compared to known methods that further oxidize disulfides to S-oxides and other byproducts.
- Natarajan, Palani,Sharma, Himani,Kaur, Mandeep,Sharma, Pooja
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supporting information
p. 5578 - 5582
(2015/09/21)
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- A diphenyl ether derived bidentate secondary phosphine oxide as a preligand for nickel-catalyzed C-S cross-coupling reactions
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A new bidentate secondary phosphine oxide (SPO) was synthesized from diphenyl ether via ortho-lithiation, phosphorylation with PhP(Cl)NEt2, and hydrolysis in an acidic medium. Nickel(0) species ligated with this new SPO was established as a mor
- Wellala, Nadeesha P. N.,Guan, Hairong
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p. 10802 - 10807
(2015/11/17)
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- Electrochemical transformation of diazonium salts into diaryl disulfides
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Electrolyses of aryldiazonium tetrafluoroborates in CS2/EtOH and Bu4NClO4, as the solvent-supporting electrolyte system, led to the corresponding diaryl disulfides in good yields.
- Barba, Fructuoso,Ranz, Fernando,Batanero, Belen
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experimental part
p. 6798 - 6799
(2010/04/27)
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- Novel photoreaction using diphenyl disulfide derivatives: Photoinduced oxidation of allyl alcohol
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Allyl alcohols are oxidized to acrylaldehydes using diphenyl disulfide derivatives upon photoirradiation. The reaction occurs via α-hydrogen abstraction by a sulfanyl radical. Interestingly, the oxidation reaction occurs in moderate yield when a dendrimer disulfide is used as a mediator.
- Tsuboi, Takaaki,Takaguchi, Yutaka,Tsuboi, Sadao
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experimental part
p. 361 - 368
(2009/04/07)
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- Cyclization of N-butyl-4-pentenylaminyl: Implications for the cyclization of alkenylaminyl radicals
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The utility of arenesulfenamides as aminyl radical precursors has been clearly demonstrated. The cyclization of N-butyl-4-pentenylaminyl is shown to be a slow and irreversible process that is accelerated significantly by small amounts of bis(tributyltin) oxide.
- Maxwell, Brendan J.,Tsanaktsidis, John
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p. 4276 - 4283
(2007/10/03)
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- Ion-radical perfluoroalkylation. Part 11. Perfluoroalkylation of thiols by perfluoroalkyl iodides in the absence of initiators
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Perfluoroalkylation of aliphatic, aromatic and heterocyclic thiols by perfluoroalkyl iodides in the presence of Et3N appears to occur spontaneously under daylight or the usual laboratory lighting conditions at 20-22 deg C and is complete in 10-15 min to 2-3 h.An exception to this rule are thiols with a low nucleophilicity.The reaction is accompanied by thiol oxidation (2percent-3percent) and depends directly on the temperature, lighting, solvent polarity and electronic properties of the perfluoroalkylating agents and of the thiol substituents.At the same time, formation of diaryl disulphides frequently occurs contrary to above rules.The reaction mechanism is discussed. - Keywords: Ion-radical perfluoroalkylation; Thiols; Perfluoroalkyl iodides; Reaction mechanism; Nucleophilicity; NMR spectroscopy
- Boiko, V. N.,Shchupak, G. M.
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p. 207 - 212
(2007/10/02)
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- Aryl alkenoic acid derivatives as leukotriene antagonists
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Aryl alkenoic acid derivatives, and physiologically acceptable salts thereof, are provided which are potent leukotriene antagonists and may be used for the treatment of circulatory diseases and preferably for respiratory diseases such as asthma. The deriv
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- Quinazoline Antifolate Thymidylate Synthase Inhibitors: Bridge Modifications and Conformationally Restricted Analogues in the C-2-Methyl Series
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Several C2-methylquinazoline-based antifolates (14-26) have been prepared in which the C9,N10 bridge has been replaced by the reversed N9,C10 unit.This series was extensively studied by incorporating further substituents at N9 and C10 as well as by modifications to the p-aminobenzoate ring.The C-2-methylquinazoline analogues 29, 30, and 31 containing the methyleneoxa, methylenethia, and thia bridge units were also synthesized.In general these isosteric replacements of the bridge unit in the parent C2-methyl-N10-propargylquinazoline antifolate 2 were much less potent as inhibitors of isolated thymidylate synthase (TS) but several were at least as potent as inhibitors of L1210 cell growth in culture.The fusion of the p-aminobenzoate ring into the bicyclic systems 75 and 76 also reduced activity against TS but again gave highly cytotoxic compounds.The cytotoxicities were largely prevented by thymidine, confirming that TS in the major locus.
- Marsham, Peter R.,Jackman, Ann L.,Hayter, Anthony J.,Daw, Melanie R.,Snowden, Jayne L.,et al.
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p. 2209 - 2218
(2007/10/02)
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- The Methyl Group as A Protecting Group for Arylthiols: A Mild and Efficient Method for the Conversion of Methyl Aryl Sulfides to Arylthiols
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Methyl aryl sulfides are converted in a mild, "one-pot", three step procedure via Pummerer rearrangement of the corresponding sulfoxides, and without purification of intermediates, to provide arylthiols in excellent yields.
- Young, Robert Norman,Gauthier, Jacques Yves,Coombs, William
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p. 1753 - 1756
(2007/10/02)
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- Investigations on Benzothiirene
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Thermolysis and photolysis of 1,2,3-benzothiadiazole 10c furnish the products 11c - 15c. 13C-labelling experiments demonstrate that an intermediate benzothiirene 1c is not formed.Isotopomeric reaction products are due to H-shifts.Electron withdrawing ester groups in 6-position enable the ring closure to the substituted benzothiirenes 1d, e on the photochemical but not on the thermal route.A proof is given by an extensive study of the disulfides 14d, e, 14d', e', and 14d'', e'', generated in the thermolysis, photolysis and by an independent procedure.The results are based on 13C and 1H NMR measurements.Unequivocal signal correlations were made by deuterations and heteronuclear double resonances.
- Meier, Herbert,Konnerth, Ursula,Graw, Sylvia,Echter, Toni
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p. 107 - 126
(2007/10/02)
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