Phenylsulfanyl Research Articles

Synthesis and Reactivity of Weiss Diketone Derivative Bearing Four Phenylsulfanyl Groups

AbstractA bicyclo[3.3.0]octane‐3,7‐dione, bearing four phenylsulfanyl (PhS) groups at the diagonal α‐positions of the carbonyls, was synthesized as a key intermediate useful for exploring the regioselective transformations of symmetrical Weiss diketone. Tetra‐PhS‐substituted bicyclo[3.3.0]octane‐3,7‐dione was prepared by deprotonation of the Weiss diketone, using LDA in the presence of PhSSO2Ph. The tetra‐PhS‐substituted derivative thus obtained served as a scaffold for further regioselective base‐promoted enolization. Furthermore, the tetra‐PhS‐substituted Weiss diketone underwent an unexpected base‐promoted rearrangement to form isomeric tetra‐PhS‐substituted bicyclo[3.3.0]octane‐3,7‐dione through migration of PhS groups, likely through an interrupted Favorskii rearrangement.

Novel Microtubule-Interacting Phenoxy Pyridine and Phenyl Sulfanyl Pyridine Analogues for Cancer Therapy

Current microtubule inhibitory agents used in the clinic to treat cancer have severe side effects, and development of resistance is frequent. We have evaluated the antitumor effect of a novel 30-compound library of phenoxy pyridine and phenyl sulfanyl pyridine derivatives. MTT assays revealed that, of all 30 compounds tested, compounds 2 and 3 showed the largest decrease in proliferation (low muM range) against Panc1 and HS766T human pancreatic cancer cells. Flow cytometry experiments with MCF7 breast cancer cells showed a G2/M arrest comparable to that of colcemid. Immunofluorescence staining demonstrated complete disappearance of intracellular microtubules. Tubulin assembly assays, however, showed a dose-dependent decrease in tubulin assembly with compound 3 that seemed limited to about 50% of the control reaction. With compound 2 treatment, there was only a delay in the onset of assembly, with no effect on the extent of the reaction. Taken together, our results show that these novel microtubule inhibitors have promising anticancer activity and can be potentially used to overcome paclitaxel resistance in the clinical setting.

Synthesis and Structure−Activity Relationships of 4-alkynyloxy Phenyl Sulfanyl, Sulfinyl, and Sulfonyl Alkyl Hydroxamates as Tumor Necrosis Factor-α Converting Enzyme and Matrix Metalloproteinase Inhibitors

A series of 4-alkynyloxy phenyl sulfanyl, sulfinyl and sulfony alkyl and piperidine-4-carboxylic acid hydroxamides were synthesized. Their structure-activity relationships, against tumor necrosis factor-alpha (TACE) and matrix metalloproteinase (MMP) inhibitor activities, are presented by investigating the oxidation state on sulfur and altering the P1' substituent. The sulfonyl derivatives 20-24 carrying a 4-butynyloxy moiety were selective TACE inhibitors over the MMPs tested. The sulfinyl derivatives showed a preference for a specific oxidation on sulfur as in compounds 25-28. The selectivity over MMPs was also demonstrated in the sulfonyl series. The enhanced cellular activity was achieved upon incorporating a butynyloxy substituent in the piperidene series. Compounds 64 and 65 were potent inhibitors of TNF-alpha release in the mouse at 100 mg/kg po.

1,2‐Migration of the Thio Group in Allenyl Sulfides: Efficient Synthesis of 3‐Thio‐Substituted Furans and Pyrroles.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Asymmetric Synthesis of Tetrahydropyrans with Competitive [1,2]‐Phenylsulfanyl (PhS) Migrations.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Asymmetric Synthesis of Tetrahydrofurans by Competitive [1,2]‐Phenylsulfanyl (PhS) Migrations under Thermodynamic Control.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Scope and Limitation of the [1,2]‐Phenylsulfanyl (PhS) Migration in the Synthesis of Tetrahydrofurans and Tetrahydropyrans from Common Triol Precursors.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Asymmetric synthesis of tetrahydrofurans by competitive [1,2]-phenylsulfanyl (PhS) migrations under thermodynamic control

Triols were prepared in enantiomerically enriched form by a short route that included a Sharpless asymmetric dihydroxylation; treatment of these triols with toluene-p-sulfonic acid gave THFs as thermodynamic products.

Scope and limitation of the [1,2]-phenylsulfanyl (PhS) migration in the synthesis of tetrahydrofurans and tetrahydropyrans from common triol precursors

Triols containing three secondary hydroxy groups were rearranged using either (i) toluene-p-sulfonic acid or (ii) trimethyl orthoacetate–pyridinium toluene-p-sulfonate followed by toluene-p-sulfonic acid

Asymmetric synthesis of tetrahydropyrans with competitive [1,2]-phenylsulfanyl (PhS) migrations

Enantiomerically enriched triols were treated with trimethyl orthoacetate and pyridinium toluene-p-sulfonate to give a mixture of unrearranged THF and rearranged THP; treatment of the product mixture with toluene-p-sulfonic acid equilibrated the mixture to the THP.

ChemInform Abstract: Asymmetric Synthesis of Tetrahydrofurans and Tetrahydropyrans with Competitive [1,2]‐Phenylsulfanyl (PhS) Migration. Part 2. Synthesis of Protected Tetrahydropyrans.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Scope and Limitation of the [1,2]‐Phenylsulfanyl (PhS) Migration in the Asymmetric Synthesis of Tetrahydrofurans and Tetrahydropyrans from Common Triol Precursors.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Asymmetric Synthesis of Tetrahydrofurans and Tetrahydropyrans with Competitive [1,2]‐Phenylsulfanyl (PhS) Migrations. Part 1. Thermodynamic Control.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Asymmetric synthesis of tetrahydrofurans and tetrahydropyrans with competitive [1,2]-phenylsulfanyl (PhS) migrations (I): thermodynamic control

Triols were prepared in enantiomerically enriched form by a short route that included a Sharpless asymmetric dihydroxylation; treatment of these triols with toluene p-sulfonic acid gave THFs as thermodynamic products.

Asymmetric synthesis of tetrahydrofurans and tetrahydropyrans with competitive [1,2]-phenylsulfanyl (PhS) migration (II): synthesis of protected tetrahydropyrans

Enantiomerically enriched triols were treated with trimethylorthoacetate and pyridinium toluene p-sulfonate to give a mixture of unrearranged THF and rearranged THP; treatment of the product mixture with toluene p-sulfonic acid equilibrated the mixture to the THP.

Scope and limitation of the [1,2]-phenylsulfanyl (PhS) migration in the asymmetric synthesis of tetrahydrofurans and tetrahydropyrans from common triol precursors

Triols containing three secondary hydroxy groups were reacted with either (i) toluene p-sulfonic acid or (ii) trimethylorthoacetate–pyridinium toluene p-sulfonate followed by toluene p-sulfonic acid.

ChemInform Abstract: Kinetic and Thermodynamic Control in the Synthesis of Tetrahydro‐pyrans and ‐furans from 1,4‐Diols by Stereospecific Phenylsulfanyl (PhS) Migration: Competition Between exo and endo Transition States and Between [1,2] and [1,4] Sulfanyl Participation.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Kinetic and Thermodynamic Control in the Synthesis of Tetrahydro-Pyrans and -Furans from 1,4-Diols by Stereospecific Phenylsulfanyl (PhS) Migration: Competition Between exo and endo Transition States and between [1,2] and [1,4]Sulfanyl Participation

The factors controlling the cyclisation of 1,4-diols with PhS migration to give THPs rather than THFs are reassessed. Furthermore we provide evidence for a competition between [1,2] and [1,4] sulfanyl participation and cyclisation onto a five membered cyclic sulfonium salt.

Kinetic and thermodynamic control in the stereospecific synthesis of cyclic ethers via phenylsulfanyl (PhS) migration

The factors controlling the stereospecific cyclisation of 1,3-diols with PhS migration to give THFs rather than oxetanes are reassessed in the light of evidence that these reactions are under thermodynamic control. Rearrangement of cyclic sulfites gives the nearest approach to kinetic control.