Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides

Cumpstey, Ian

doi:10.1016/j.carres.2009.09.008

Cited by 16 publications

(5 citation statements)

References 90 publications

(160 reference statements)

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“…Although the formation of sec – sec ethers is well known, only a few examples lead to densely functionalised compounds 20,41,42. The main problem in the required S N 2 type reaction is the use of highly substituted, sterically hindered starting materials.…”

Section: Resultsmentioning

confidence: 99%

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A synthetic cyclitol-nucleoside conjugate polyphosphate is a highly potent second messenger mimic

Döhle

Mills

et al. 2019

Chem. Sci.

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Section: Resultsmentioning

confidence: 99%

“…The main problem in the required S N 2 type reaction is the use of highly substituted, sterically hindered starting materials. A limited number of electrophiles, such as a triflate within a rigid organic framework have been used successfully 20,41. Compound 14 could be assembled in two steps from the ribose orthoester derivative 15 .…”

Section: Resultsmentioning

confidence: 99%

A synthetic cyclitol-nucleoside conjugate polyphosphate is a highly potent second messenger mimic

Döhle

Mills

et al. 2019

Chem. Sci.

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“…Ogawa has extensively used epoxide-opening reactions as a coupling method to access N - and O -linked pseudodisaccharides based on carbapyranoses [10]. The epoxides were opened by amines in uncatalysed reactions, or by alcohols under Lewis acidic, but more usually basic, conditions.…”

Section: Introductionmentioning

confidence: 99%

Carbasugar analogues of galactofuranosides: α-O-linked derivatives

Frigell¹,

Cumpstey²

2010

Beilstein J. Org. Chem.

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Using an indirect method, we have synthesised α-linked carbasugar analogues of galactofuranosides for the first time. Ring opening of a β-talo configured carbasugar 1,2-epoxide by alcohol nucleophiles under Lewis acidic conditions proceeded with very good regioselectivity to give α-talo configured C1-substituted ethers with a free OH-group at the C2 position. Inversion of configuration at C2 by an oxidation-reduction sequence gave the α-galacto configured carbahexofuranose C1 ethers. A carbadisaccharide corresponding to the Galf(α1→3)Manp substructure from Apodus deciduus galactomannan was synthesised to exemplify the method.1127

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“…Herein, we report an unexplored attractive application of these SILs as solvents/Lewis acids that are able to efficiently promote the ring opening of epoxides due to the coordination between the substrate and the cationic species present into the glyme [37]. In particular, in the context of a research program concerning the discovery of new methodologies for the synthesis of carbasugars [38,39,40,41,42], the Li[NTf 2 ]/tetraglyme ( [Li(G4)]TFSI ) system was found to promote a highly regio- and stereoselective ring opening of carbapyranoses 1,2-epoxides with an α-gluco configuration, such as those represented in Scheme 1. These substrates can be used as a pseudo glucosyl donor for the synthesis of C(1)-carbasugars featuring the challenging pseudo β-glucosidic bond.…”

Section: Introductionmentioning

confidence: 99%

Remarkable Effect of [Li(G4)]TFSI Solvate Ionic Liquid (SIL) on the Regio- and Stereoselective Ring Opening of α-Gluco Carbasugar 1,2-Epoxides

et al. 2019

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Carba analogues of biologically relevant natural carbohydrates are promising structures for the development of future drugs endowed with enhanced hydrolytic stability. An open synthetic challenge in this field is the optimization of new methodologies for the stereo- and regioselective opening of α-gluco carbasugar 1,2-epoxides that allow for the preparation of pseudo mono- and disaccharides of great interest. Therefore, we investigated the effect of Lewis acids and solvate ionic liquids (SILs) on the epoxide ring opening of a model substrate. Of particular interest was the complete stereo- and regioselectivity, albeit limited to simple nucleophiles, toward the desired C(1) isomer that was observed using LiClO4. The results obtained with SILs were also remarkable. In particular, Li[NTf2]/tetraglyme ([Li(G4)]TFSI) was able to function as a Lewis acid and to direct the attack of the nucleophile preferentially at the pseudo anomeric position, even with a more complex and synthetically interesting nucleophile. The regioselectivity observed for LiClO4 and [Li(G4)]TFSI was tentatively ascribed to the formation of a bidentate chelating system, which changed the conformational equilibrium and ultimately permitted a trans-diaxial attack on C(1). To the best of our knowledge, we report here the first case in which SILs were successfully employed in a ring-opening process of epoxides.

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Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides

Cited by 16 publications

References 90 publications

A synthetic cyclitol-nucleoside conjugate polyphosphate is a highly potent second messenger mimic

A synthetic cyclitol-nucleoside conjugate polyphosphate is a highly potent second messenger mimic

Carbasugar analogues of galactofuranosides: α-O-linked derivatives

Remarkable Effect of [Li(G4)]TFSI Solvate Ionic Liquid (SIL) on the Regio- and Stereoselective Ring Opening of α-Gluco Carbasugar 1,2-Epoxides

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