Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors

Chéry, Florence; Cassel, Stéphanie; Wessel, Hans Peter; Rollin, Patrick

doi:10.1002/1099-0690(20021)2002:1<171::aid-ejoc171>3.0.co;2-7

Cited by 24 publications

(15 citation statements)

References 30 publications

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“…They are obtained via reaction of choramine-T (the sodium salt of N-chloro-p-toluenesulfonamide) with thioglycosides under phase transfer conditions [84]. These derivatives can be considered as nitrogeneous analogs of sulfoxides and, as such, were proposed to serve as donors in activated glycosylation reactions similar to Kahne's sulfoxide method [85].…”

Section: Ii) the Sulfenamide (-S-n-) Linkagesupporting

confidence: 89%

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Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Varela¹

2006

COC

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Thiooligosaccharides display inhibitory activity against glycoside hydrolases and they constitute a valuable tool for structural biology. The construction of the interglycosidic linkage, in which the oxygen atom is replaced by sulfur, usually involves one of the following reactions: i) nucleophilic displacement of good leaving groups in a carbohydrate moiety by a sugar thiol, ii) Michael and Michael-type additions of sugar thiols to unsaturated acceptors, iii) ring-opening of aziridines and oxiranes by thiosugars, iv) enzyme-catalyzed couplings of thiosugar moieties. The application of these reactions for the syntheses of thiooligosaccharides are surveyed, and the biological activities of the resulting products briefly described. Carbohydrate structures incorporating three-bond glycosidic linkages with two heteroatoms are uncommon in Nature. The -N-O-interglycosidic bond in the oligosaccharide part of enediyne antibiotics is partly responsible for their potent antitumor activities. The disulfide bond which plays an essential role in proteins has recently been introduced as an interglycosidic connecting motif. The sulfenamide functionality is the sulfur analog of the hydroxylamine type glycosidic linkages in calicheamicins. Novel glycosylation strategies have recently been developed by taking advantage of unconventional, three-bond glycosidic linkages to construct neoglycoproteins and other glycoconjugates which are increasingly important tools in glycobiology and drug discovery. To explore conformational preferences and molecular flexibility in these structures NMR spectroscopy, chiroptical methods and X-ray crystallography are being used, supplemented by molecular modelling calculations. The structural features will be briefly discussed with relevance to biological interactions such as enzyme binding.

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Section: Ii) the Sulfenamide (-S-n-) Linkagesupporting

confidence: 89%

“…These derivatives can be considered as nitrogeneous analogs of sulfoxides and, as such, were proposed to serve as donors in activated glycosylation reactions similar to Kahne's sulfoxide method [85]. Softer Lewis acids, such as Cu(OTf)2, proved to be efficient promoters in these glycosylation reactions [84].…”

Section: Ii) the Sulfenamide (-S-n-) Linkagementioning

confidence: 99%

Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Varela¹

2006

COC

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“…85,86 The analogous sulfimides, formed from the thioglycoside by reaction with chloramine T, can also be used for glycosylation, upon activation with Cu(OTf) 2 /CuO. 87 Sulfimides have been used for glycosylation of p-methoxyphenol in excellent yields (Scheme 23).…”

Section: Glycosyl Sulfoxides and Sulfimidesmentioning

confidence: 99%

Aromatic O-glycosylation

Jacobsson

Malmberg

Ellervik

2006

Carbohydrate Research

113

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“…The chemistry of sulphimides is a subject of substantial interest, focused on their synthetic applications as well as pharmacological properties [43][44][45] . Less attention has been paid to the reduction of sulphimides to sulphides, although a few reagents have been used to achieve this reduction satisfactorily (Table 4).…”

Section: Reduction Of Sulphimidesmentioning

confidence: 99%

“…Sulphoxides and sulphimides are important reagents and/or intermediates in organic chemistry [43][44][45]52,53 . Moreover, this group of organo-sulphur compounds also shows very interesting biological and/or pharmacological activity (Table 8) 45,54,55 .…”

Section: Analytical Application Of Tfaa-i For Determination and Detecmentioning

confidence: 99%

Trifluoroacetic anhydride-sodium iodide reagent. Nature and applications

Kudzin¹,

Kudzin²,

Drabowicz³

et al. 2007

Arkivoc

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Trifluoroacetic anhydride -sodium iodide mixture (TFAA-NaI; TFAA-I) reacts with several compounds bearing semipolar X-O bond, usually in the mode of deoxygenation, with liberation of iodine. The results of systematic investigations of the TFAA-I-reaction with various types of S-oxo and N-oxo compounds were discussed. The majority of these reactions are characterized by quantitative course, with respect to both X-O substrate transformation as well as to the amounts of liberated iodine. On this basis, a variety of sulphoxides and sulphimides were successfully reduced to sulphides and/or arene-N-oxides to amines, using TFAA-I at ambient temperature. Arene-and alkyl-sulphonic acids were reduced to the corresponding thiol derivatives in moderate yields. Stoichiometric course of the TFAA-I reaction with several S-oxo and N-oxo compounds gave origin to their analytical determinations. Thus, due to stoichiometric amounts of iodine formed from sulphoxides, sulphimides, arene-N-oxides, nitrones and nitroxide radicals, and nitroso compounds -the TFAA-I reagent can be applied to their analytical determination (titrimetric on µmol and spectrometric on nmol scale) and/or TLC detection.

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Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors

Abstract: We introduce a convenient synthesis of anomeric sulfimides, the ability of which to act as glycosyl donors has been tested with various thiophilic reagents and acceptors.

Cited by 24 publications

References 30 publications

Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Aromatic O-glycosylation

Trifluoroacetic anhydride-sodium iodide reagent. Nature and applications

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