Efficient Synthesis of Unsymmetrical Disulfides through Sulfenic Acids

Aversa, M. C.; Barattucci, Anna; Bonaccorsi, Paola

doi:10.1002/ejoc.200900986

Cited by 29 publications

(15 citation statements)

References 34 publications

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“…Condensation of sulfenic acids with thiols, employed until the last decade only to demonstrate indirectly the in situ generation of these unstable intermediates, has found its application in the disulfide bond formation (b in scheme 3). The mild and effective synthesis of a wide range of disulfides bearing two different R groups at the disulfane moiety was accessible [21]. In this short review of our work, the syntheses of a variety of biologically relevant sulfoxides, sulfones and disulfides are reported.…”

Section: Scheme 1 Generation Of Transient Sulfenic Acidsmentioning

confidence: 99%

“…In scheme 6 the synthetic pathways for the synthesis of thiosaccharides 17 and 18 are shown. Compound 18 was obtained by thermolysis at 40°C of sulfoxide 11 in DCM, in the presence of glucopyranoside 14 [21]. The concerted addition of the in situ generated glucosulfenic acid 12 into the triple bond of compound 14 afforded an epimeric mixture of thiosaccharides 16, that was oxidized to the unique enantiomerically pure thiosaccharide 17.…”

Section: Thiosaccharidesmentioning

confidence: 99%

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Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products

Barattucci

Aversa

Mancuso

et al. 2018

Preprint

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Sulfenic acids as small molecules are too unstable to be isolated and their transient nature offers the possibility to involve them in concerted processes that lead to the obtainment of functional groups such as sulfoxides, sulfones and disulfides. All these functions are present in a number of natural and synthetic drugs and can represent structural motives inducing biological relevant properties. In this small review the generation and reactions of sulfenic acid bearing naturally occurring residues are described. Carbohydrate and aminoacid-derived sulfenic acids have been used in concerted addition to triple bonds to obtain alliin derivatives and thiosugars in enantiomerically pure form. Glycoconjugates with sulfinyl, sulfonyl and disulfane functional groups and pyridine-derived disulfides have been obtained from bis and tris-sulfinyl precursors of sulfenic acids. Small families of such compounds have been subjected to preliminary biological tests. Starting from the evidence that the control of molecular architecture and the presence of suitable functional groups can play a significant role on the exhibition of biological properties, apoptotic effects on malignant cells by glycoconjugates and inhibitory activity against the important human pathogen S. aureus by pyrimidine-derived disulfides have been found.

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Section: Scheme 1 Generation Of Transient Sulfenic Acidsmentioning

confidence: 99%

Section: Thiosaccharidesmentioning

confidence: 99%

Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products

Barattucci

Aversa

Mancuso

et al. 2018

Preprint

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“…[23] In addition, glycosyl thiols are at the base of a one-pot methodology that uses 1-chlorobenzotriazole as an in situ trapping/oxidizing agent [24] and also in a more elaborate three-step procedure in which sulfenic acids are generated from suitable sulfonyl intermediates. [25] Finally, mixtures of structurally different glycosyl thiols can be coupled through a disulfide bond by an adaptation of the DEAD-based oxidation methodology discussed above [20] and also by using 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) as an oxidant. [21] As part of ongoing projects in our laboratories, herein we report on the chemical behavior and synthetic applications of S-glycopyranosyl-N-monoalkyl DTCs, compounds not previously exploited despite their easy preparation by the classic nucleophilic substitution methodology of 1-halo sugars with N-alkyl dithiocarbamate salts.…”

Section: Introductionmentioning

confidence: 99%

Masked Thiol Sugars: Chemical Behavior and Synthetic Applications of S‐Glycopyranosyl‐N‐monoalkyl Dithiocarbamates

Megia‐Fernandez

Parada-Aliste

Lopéz-Jaramillo

et al. 2013

Chemistry An Asian Journal

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The chemical behavior of S-glycopyranosyl-N-monoalkyl dithiocarbamates (DTCs) as masked 1-glycosyl thiols, easily prepared by the nucleophilic displacement of 1-halo sugars with dithiocarbamate salts of primary amines, has been studied and synthetically exploited. This behavior relies on the abstraction of the proton of the carbamate functionality that allows controlled access to thiolate sugar intermediates. The basic character of the DTC salts used as reagents leads to thiolates that evolve in situ to symmetrical diglycosyldisulfides (DGDSs) when long reaction times are allowed. Alternatively, controlled unmasking of the thiolate function can be efficiently attained by treatment with an external base of isolated anomeric glycosyl DTCs, the formation of which is prevalent when using short reaction times. In this manner, a second methodology for the preparation of symmetrical DGDSs and a chemical protocol for the S-glycosylation of any electrophilic substrate are established. The applications of this last strategy for the preparation of thioglycosyl vinyl sulfones, thiodisaccharides, and S-linked homo- and heterodivalent neoglycoconjugates are described as a proof-of-concept of the great potential of the sugar DTCs in any chemical scenario in which the covalent attachment of a thiol sugar is required. The evaluation of the biological functionality of some divalent sulfurated sugar systems is also described.

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“…Among others [ 23 ], condensation of sulfenic acids with thiols, employed until the last decade only to demonstrate indirectly the in situ generation of these unstable intermediates, has found its application in the formation of disulfide bonds ( b in Scheme 3 ). The mild and effective synthesis of a wide range of disulfides bearing two different R groups at the disulfane moiety was accessible [ 24 ].…”

Section: Introductionmentioning

confidence: 99%

Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products

et al. 2018

Self Cite

View full text Add to dashboard Cite

Sulfenic acids as small molecules are too unstable to be isolated and their transient nature offers the possibility to involve them in concerted processes that lead to the obtainment of functional groups such as sulfoxides, sulfones, and disulfides. All these functions are present in a number of natural and synthetic drugs and can represent structural motives inducing biologically relevant properties. In this small review the generation and reactions of sulfenic acid bearing naturally occurring residues are described. Carbohydrate and aminoacid-derived sulfenic acids have been used in concerted addition with triple bonds to obtain alliin derivatives and thiosugars in enantiomerically pure form. Glycoconjugates with sulfinyl, sulfonyl, and disulfane functional groups and pyridine-derived disulfides have been obtained from bis- and tris-sulfinyl precursors of sulfenic acids. Small families of such compounds have been subjected to preliminary biological tests. Starting from the evidence that the control of molecular architecture and the presence of suitable functional groups can play a significant role on the exhibition of biological properties, apoptotic effects on malignant cells by glycoconjugates and inhibitory activity against the important human pathogen S. aureus by pyrimidine-derived disulfides have been found.

show abstract

Efficient Synthesis of Unsymmetrical Disulfides through Sulfenic Acids

Cited by 29 publications

References 34 publications

Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products

Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products

Masked Thiol Sugars: Chemical Behavior and Synthetic Applications of S‐Glycopyranosyl‐N‐monoalkyl Dithiocarbamates

Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products

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