- Synthesis of 2-Thio-Substituted 1,6-Diazabicyclo[3.2.1]octane Derivatives, Potent β-Lactamase Inhibitors
-
Approval of avibactam by the FDA has led to the recognition of 1,6-diazabicyclo[3.2.1]octane (DBO) derivatives as attractive compounds for β-lactamase inhibition. We achieved a concise and collective synthesis of 2-thio-substituted DBO derivatives. The synthesis involves diastereoselective photo-induced Barton decarboxylative thiolation, which can be applied to large-scale synthesis. The DBO analogues exhibited strong inhibitory activities against serine β-lactamases and acceptable solution stabilities for clinical development.
- Aoki, Toshiaki,Fujiu, Motohiro,Komano, Kazuo,Kusano, Hiroki,Ogawa, Masayoshi,Sato, Jun,Sato, Soichiro,Shibuya, Satoru,Yamawaki, Kenji,Yokoo, Katsuki
-
-
Read Online
- Bioactive pyridine-N-oxide disulfides from allium stipitatum
-
From Allium stipitatum, three pyridine-N-oxide alkaloids (1-3) possessing disulfide functional groups were isolated. The structures of these natural products were elucidated by spectroscopic means as 2-(methyldithio)pyridine-N- oxide (1), 2-[(methylthiome
- O'Donnell, Gemma,Poeschl, Rosemarie,Zimhony, Oren,Gunaratnam, Mekala,Moreira, Joao B. C.,Neidle, Stephen,Evangelopoulos, Dimitrios,Bhakta, Sanjib,Malkinson, John P.,Boshoff, Helena I.,Lenaerts, Anne,Gibbons, Simon
-
-
Read Online
- Convenient Unsymmetrical Disulfane Synthesis: Basic Zeolite-Catalyzed Thiol-Disulfane Exchange Reaction
-
Convenient catalytic synthetic methods for the preparation of unsymmetrical disulfanes are described. Na-exchanged X type zeolite (Na-X), commercially available as MS-13X, effectively catalyzes thiol-disulfane exchange reactions with 1.0 equivalent of thi
- Yamamoto, Eiji,Kawai, Yasutaka,Takakura, Kei,Kimura, Moemi,Murayama, Haruno,Matsueda, Hironobu,Otsuki, Shujiro,Sakata, Hiroshi,Tokunaga, Makoto
-
p. 4694 - 4699
(2021/10/14)
-
- Enzyme-catalysed oxidation of 1,2-disulfides to yield chiral thiosulfinate, sulfoxide and cis-dihydrodiol metabolites
-
Enantioenriched and enantiopure thiosulfinates were obtained by asymmetric sulfoxidation of cyclic 1,2-disulfides, using chemical and enzymatic (peroxidase, monooxygenase, dioxygenase) oxidation methods and chiral stationary phase HPLC resolution of racemic thiosulfinates. Enantiomeric excess values, absolute configurations and configurational stabilities of chiral thiosulfinates were determined. Methyl phenyl sulfoxide, benzo[c]thiophene cis-4,5-dihydrodiol and 1,3-dihydrobenzo[c]thiophene derivatives were among unexpected types of metabolites isolated, when acyclic and cyclic 1,2-disulfide were used as substrates for Pseudomonas putida strains. Possible biosynthetic pathways are presented for the production of metabolites from 1,4-dihydrobenzo-2,3-dithiane, including a novel cis-dihydrodiol metabolite that was also derived from benzo[c]thiophene and 1,3-dihydrobenzo[c]thiophene.
- Boyd, Derek R.,Sharma, Narain D.,Shepherd, Steven D.,Allenmark, Stig G.,Allen, Christopher C. R.
-
p. 27607 - 27619
(2014/07/21)
-
- On the thermal Pummerer rearrangement of substituted sulfoxides
-
Sulfoxides bearing thioester and ester groups at the position under heating at ca. 140C undergo Pummerer thermal rearrangement. However, for sulfonyl sulfoxide, a complex mixture of products is formed. Plausible mechanism is advanced(equation presented. 2013
- Marzorati, Liliana,Yoshikawa, Eduardo K.C.,Braga, Ataualpa A.C.,Di Vitta, Claudio
-
p. 248 - 260
(2014/04/03)
-
- On aromatic electrophilic substitution promoted by in situ generated thionium ions
-
α-Sulfanylated α-arylacetates and -thioacetates were prepared via ethylthiomethylation reaction of aromatic compounds. These aromatic electrophilic substitutions were performed by in situ generation of the thionium ions by reacting trifluoroacetic anhydri
- Amici, Rosanaribeiro,Di Vitta, Claudio,Marzorati, Liliana
-
p. 798 - 802
(2013/04/23)
-
- Phosphine-catalyzed disulfide metathesis
-
The reaction between disulfides and phosphines generates a reversible disulfide metathesis process. The Royal Society of Chemistry 2008.
- Caraballo, Remi,Rahm, Martin,Vongvilai, Pornrapee,Brinck, Tore,Ramstroem, Olof
-
scheme or table
p. 6603 - 6605
(2009/04/20)
-
- Sulfur containing compounds
-
This invention is directed to novel and known stufur containing compounds and pharmaceutically acceptable salts thereof that have utility as antifungals and as antiproliferative agents against mammalian cells, in particular cancer cells and most particularly leukemia-derived cells. The invention provides a method for synthesizing certain of the sulfur containing compounds that is more efficient than previously known methods.
- -
-
Page/Page column 25
(2010/11/30)
-
- New and more potent antifungal bisulfides
-
From a design principle described in an earlier paper, a new series of substituted aryl methyl disulfides have been prepared and tested against Aspergillus niger and Aspergillus flavus. Methyl p-nitrophenyl disulfide is more potent (by an order of magnitude) than the fungitoxic natural product (CH3SCH2S)2. With the present rationale in hand, one can anticipate which Polycarpamine is an effective antifungal agent. CSIRO 2000.
- Baerlocher, Felix Jakob,Baerlocher, Mark Otto,Langler, Richard Francis,MacQuarrie, Stephanie Lee,Marchand, Maurice Emile
-
-
- Cleavage of S-S bond by nitric oxide (NO) in the presence of oxygen: A disproportionation reaction of two disulfides
-
Disulfide bond was cleaved by a catalytic amount of nitric oxide in the presence of oxygen, which was confirmed by experiments employing two symmetrical disulfides. The reaction resulted in the formation of unsymmetrical disulfides in nearly 50% yields. The steric hindrance of alkyl disulfide slowed the reaction rate, and an electron-donating group on the aryl disulfide promoted the reaction. The substituent and S-nitrosothiol effects suggested that the reaction was initialized with an oxidative process by NO+.
- Tsutsumi,Itoh,Ohsawa
-
p. 1524 - 1528
(2007/10/03)
-
- Disproportionation reaction of disulfides promoted by nitric oxide (NO) in the presence of oxygen
-
Two disulfides brought about disproportionation reaction to afford an unsymmetrical disulfide in 50% yield with a catalytic amount of nitric oxide in the presence of oxygen. The reaction proceeded faster when alkyl disulfides were employed for the reaction, and the substituent effects suggested that the reaction commenced with an oxidative process.
- Itoh, Takashi,Tsutsumi, Nozomi,Ohsawa, Akio
-
p. 2161 - 2166
(2007/10/03)
-
- A new synthesis for antifungal α-sulfone disulfides
-
An α-ester disulfide is shown to be a useful precursor for the preparation of several α-sulfone disulfides. These new α-sulfone disulfides are all fungitoxic against Aspergillus niger and Aspergillus flavus. CSIRO 1999.
- Langler, Richard Francis
-
p. 1119 - 1121
(2007/10/03)
-
- Through-bond interaction between sulfonium and sulfenyl sulfur atoms having anthracene and naphthalene spacers
-
The reaction of 9-(methylsulfinyl)-10-(methylthio)anthracene with trifluoroacetic anhydride followed by quenching with aqueous NaHCO3 gives 9,9-bis(methylthio)-10-anthraquinone. The dithia dication and/or the corresponding carbodication via thr
- Koyama, Emiko,Kobayashi, Kenji,Horn, Ernst,Furukawa, Naomichi
-
p. 8833 - 8836
(2007/10/03)
-
- A new electrochemical method of preparation of unsymmetrical disulfides
-
A new method is described for the preparation of unsymmetrical disulfides by reaction of the electrogenerated sulfenium cation R1-S+ with thiols or disulfides.
- Do, Quang Tho,Elothmani, Driss,Le Guillanton, Georges,Simonet, Jacques
-
p. 3383 - 3384
(2007/10/03)
-
- Reactions of dimethyl polysulfides with organomagnesium reagents
-
Reactions of a mixture of dimethyl polysulfides (DMPS, CH3SxCH3, x = 3 - 8) with methyl- and phenylmagnesium halides are described.The type of product obtained was dependent on the molar ratio of DMPS to Grignard reagent.When a 6:1 methyl-Grignard to DMPS ratio was used, methanethiol and dimethyl sulfide were the major products obtained after acidification of the reaction mixture.Lesser quantities of methyl-Grignard favored the formation of dimethyl sulfide, dimethyl disulfide, and H2S.Experiments with a 6:1 phenylmagnesium bromide to DMPS ratio produced benzenethiol and phenylmethyl sulfide as major products after acidification.No methanethiol was observed in these experiments.Mixtures of phenylmethyl mono-, di- and trisulfides and H2S were obtained with a 3:1 Grignard/DMPS molar ratio.From a mechanistic viewpoint, product distributions obtained from reaction of Grignard reagents with DMPS can be explained by the formation of magnesium thiolates that are most readily stabilized by adjacent structures.Experiments using phenyl Grignard reagent in limited supply suggested that the internal sulfur atoms of the polysulfide chains were more reactive.
- Clark, Peter D.,Mann, Russell S.,Lesage, Kevin L.
-
-
- Some Unusual Properties of Tris(2,6-dimethoxyphenyl)phosphine Sulfide and the Related Compounds
-
The title sulfide 3P=S reacted with acids to form a novel mercaptophosphonium salt X, solution thermolysis of which in the absence or presence of triphenylphosphine resulted in the unusual desulfurization to give the tertiary phosphonium salts X. (2,6)3P=S also reacted with alkyl iodides or bromides under mild conditions to give stable (alkylthio)phosphonium salts X (R=Me, Et, n-Bu), which reacted with thiols at room temperature in the presence of a catalytic amount of the tertiary phosphine (2,6)3P to give X and unsymmetrical disulfides.
- Wada, Masanori,Kanzaki, Mitsuyuki,Fujiwara, Masanobu,Kajihara, Kazuhisa,Erabi, Tatsuo
-
p. 1782 - 1786
(2007/10/02)
-
- A New Procedure for the Conversion of Thiols into Reactive Sulfenylating Agents
-
Thiols may be converted in high yield into unsymmetrical 2-pyridyl disulfides 3.Treatment of these with alkylating agents (e.g., alkyl fluorosulfonates or oxonium salts) affords the corresponding N-alkylpyridyl disulfides 4, which are potent sulfenylating agents (Scheme II) and react smoothly with a variety of sulfur nucleophiles (e.g., thiols, thiones, thioamides, dithiocarbamates, thiocyanate, etc.) to afford disulfides, with amines to afford sulfenamides, and with β-diketones to afford sulfides.This new method is particularly well-suited to the preparation of unsymmetrical disulfides and sulfenamides from complex and otherwise r eactive thiols.
- Barton, D. H. R.,Hesse, R. H.,O'Sullivan, A. C.,Pechet, M. M.
-
p. 6697 - 6702
(2007/10/02)
-
- Formation of Stable Aryldisulphide Ions in Dimethylacetamide from the Reaction of Sulphur with Thiolate Ions
-
The conditions for the formation of aryldisulphide ions, RS2- during the direct reaction of sulphur with thiolate ions RS- have been studied by the use of spectroelectrochemistry in dimethylacetamide.The series of derivatives examined was R = p-tolyl (1), phenyl (2), 8-quinolyl (3), 2- and 4-pyridyl (4), (5), N-oxido 4-pyridyl (6), 2- and 4-nitrophenyl (7), (8), and 2-(5-nitropyridyl) (9).Sulphur reaction leads to RS2- ions and preceded the oxidation to diaryldisulphide RS2R and polysulphide ions Sx-.With derivatives (1)-(3), both reactions are successive and practically stoicheiometric, while for derivatives containing electron-withdrawing groups (6)-(9), the equilibrium constants have been measured.Analysis of the reaction products by methylation of several solutions of thiolate ions in the presence of sulphur confirmed the possibility of obtaining aryldisulphide ions stabilized in aprotic dipolar media.
- Benaichouche, Meriem,Bosser, Gerard,Paris, Jacky,Auger, Jacques,Plichon, Vincent
-
-
- Facile Synthesis of Alkylthiophosphonium Salts of Tris(2,6-dimethoxyphenyl)phosphine and Their Reactions with Thiols
-
Tris(2,6-dimethoxyphenyl)phosphine sulfide reacted with alkyl iodides or bromides under mild conditions to give stable alkylthiophosphonium salts, which reacted with thiols at room temperature in the presence of a catalytic amount of tris(2,6-dimethoxyphenyl)phosphine to give the tertiary phosphonium salt and unsymmetrical disulfides.
- Wada, Masanori,Kanzaki, Mituyuki,Fujiwara, Masanobu,Kajihara, Kazuhisa,Erabi, Tatsuo
-
p. 867 - 870
(2007/10/02)
-
- SYNTHESIS OF DISULPHIDES AND TRISULPHIDES via ORGANOSILICON COMPOUNDS
-
Silyl sulphides 2a-b smoothly react with thiolsulphinates 1a-c and thiolsulphonates 6a-c to give unsymmetrical disulphides under mild conditions and in very good yields.The "neutral" conditions used allow one to avoid any side reactions and subsequent randomization of the products.When bis(trimethylsilyl)sulphide, 8, is used, symmetrical trisulphides may be obtained under the same experimental conditions.
- Capozzi, Giuseppe,Capperucci, Antonella,Degl'Innocenti, Alessandro,Duce, Rosa Del,Menichetti, Stefano
-
p. 421 - 426
(2007/10/02)
-
- SILICON IN ORGANOSULPHUR CHEMISTRY. Part 2. SYNTHESIS OF UNSYMMETRICAL DISULPHIDES
-
Unsymmetrical aryl- and alkyl-disulphides are prepared from silylsulphides and thiosulphinates or thiosulphonates.Silyl sulphinic esters are also obtained in the reaction of the thiosulphonates.
- Capozzi, Giuseppe,Capperucci, Antonella,Degl'Innocenti, Alessandro,Duce, Rosa Del,Menichetti, Stefano
-
p. 2995 - 2998
(2007/10/02)
-
- ZUR 1,3-THIAZIN-RINGKONTRAKTION: NEUE ASPEKTE DURCH 6-DONORSUBSTITUENTEN
-
The reaction of 6-morpholino- and 6-phenylthio-6H-1,3-thiazines with BuLi at low temperature manifests striking differences to the behaviour of 2,4,6-triaryl species: Ring contraction to the pyrrol ring system involves predominantly S-transfer into exocyclic position instead of immediate S-extrusion.The results are discussed in relation to ?-donor effects by 6-heterosubstituents.
- Spitzner, Roland,Schroth, Werner
-
p. 3971 - 3974
(2007/10/02)
-
- Reactions of Tetraphosphorus Trisulphide with Organic Disulphides under Ultraviolet Irradiation, and with Sulphuryl Chloride
-
P4S3 under glass-filtered u.v. irradiation is rapidly cleaved by alkyl and aryl disulphides to give tetrathiophosphate esters, SP(SR)3, and trithiophosphite esters, P(SR)3 (R = Me or Ph), in quantitative yield, as measured in the product mixture by 31P and 1H n.m.r. spectroscopy.No sulphurisation of P4S3 was found.In a competition reaction, MeSSMe and PhSSPh reacted to a similar extent with P4S3 to give all eight possible products SxP(SPh)n(SMe)(3-n) (x = O or 1, n = 0-3) in relative quantities within each oxidation state approximating to a statistical distribution of ligands, but there was more MeS substitution of the phosphorus (V) produts and more PhS substitution of the phosphorus(III) products.Reaction of MeSSPh with P4S3 gave similar results.Redistribution of ligands took place when a mixture of P(SMe)3 and P(SPh)3 was photolysed, and photolysis of a mixture of P(SMe)3 and MeSSPh caused the PhS group to be distributed between the trithiophosphite and disulphide sites.P(SMe)3 and P(SPh)3 were not sulphurised by MeSSMe and PhSSPh respectively, but P(SMe)3 was sulphurised to SP(SMe)3 to a small extent by MeSSPh.P4S3 is similarly cleaved by sulphuryl chloride, but under thermal conditions, to give SPCl3 and PCl3, with no evidence for intermediates.
- Musa, Faleh H.,Tattershall, Bruce W.
-
p. 1517 - 1520
(2007/10/02)
-
- Oxidation of Unsymmetrical Disulfide and Thiosulfinic S-Esters with Peroxy Acids. Search for Formation of α-Disulfoxide as An Intermediate in the Electrophilic Oxidation of Thiosulfinic S-Ester
-
Oxidation of an unsymmetrical disulfide, methyl phenyl disulfide, with peroxy acids takes place mainly at more electron-rich sulfur atom to form thiosulfinic S-ester at the first stage, while oxidation of unsymmetrical thiosulfinic S-ester with peroxy acids gives usually four thiosulfonic S-esters, together with sulfinic and sulfonic acids, further oxidation products.Oxidation of S-methyl benzenethiosulfinate 6 affords, as one of the products, S-phenyl methanethiosulfonate 11, in which the original sulfinyl oxygen is brought into methanesulfonyl group.A small amount of S-phenyl benzenethiosulfonate 9 (or benzenesulfonic acid 15) is obtained in the oxidation of S-phenyl methanethiosulfinate 7. 18O-Label of the starting thiosulfinic S-ester 6 was found to be incorporated to some extents into all four products, i.e. 8-11, while a part of 18O-label of S-phenyl methanethiosulfinate 7 was also observed in S-phenyl benzenethiosulfonate 9 and benzensulfonic acid 15, although most of 18O-label of 7 was incorporated into S-phenyl methanethiosulfonate 11.Thiosulfinic S-esters are stable and do not undergo disproportionation and 18O-exchange under the conditions.These observations suggest the formation of α-disulfoxide as an intermediate in the oxidation of thiosulfinic S-ester to thiosulfonic S-ester, especially in the oxidation of 6, although no peak corresponding to α-disulfoxide was observed directly in the NMR spectra taken during the oxidations of a few thiosulfinic S-esters with peroxy acid.Mechanism of the oxidation is discussed.
- Oae, Shigeru,Takata, Toshikazu,Kim, Yong Hae
-
p. 2484 - 2494
(2007/10/02)
-
- Desulfuration Using Plasma Techniques, III. - Reaction of Thioethers
-
Plasma desulfurations were tested with nine thioethers.While aliphatic, as well as aromatic thioethers and thiophene react easily, benzothiophenes are hard to desulfurize.Predominant reaction products are low molecular alkenes and alkanes (Table 1).Addition of oxygen greatly improves the results (Table 2).
- Suhr, Harald,Henne, Peter,Iacocca, Diodoro,Ropero, Marcos J.
-
p. 441 - 446
(2007/10/02)
-