Stereoselective Synthesis ofcarba- andC-Glycosyl Analogs of Fucopyranosides

Carpintero, Mercedes; Jaramillo, Carlos; Fernández-Mayoralas, Alfonso

doi:10.1002/1099-0690(200004)2000:7<1285::aid-ejoc1285>3.0.co;2-z

Cited by 31 publications

(12 citation statements)

References 44 publications

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“…in DMF at 100°C gave [20] the substitution product 22 (Scheme 4, 50%) and the elimination product 21 (46%), demonstrating that 19 is a poor substrate for moderate nucleophiles. Deprotection of 22 with 4  hydrochloric acid in aqueous THF gave free 5a-carba-α--fucopyranose [21,22] 4 (65%). Azidolysis of 19 with sodium azide (5 mol-equiv.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Biological Evaluation of α-L-Fucosidase Inhibitors: 5a-Carba-α-L-fucopyranosylamine and Related Compounds

Ogawa¹,

Maruyama

Odagiri

et al. 2001

Eur. J. Org. Chem.

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Keywords: Carbohydrates / Cyclitols / Carba sugars / 5a-Carba-α--fucopyranosylamine / Enzyme inhibitors / α--Fucosidase inhibitors 5a-Carba-α-L-fucopyranosylamine (5), an α-glucosidase inhibitor validamine analog possessing an α-L-fucose-type structure, and four related compounds (4 and 6−8) were synthesized and their glycosidase inhibitory potential determined. Carbafucosylamine has already been shown to pos-

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Section: Resultsmentioning

confidence: 99%

Synthesis and Biological Evaluation of α-L-Fucosidase Inhibitors: 5a-Carba-α-L-fucopyranosylamine and Related Compounds

Ogawa¹,

Maruyama

Odagiri

et al. 2001

Eur. J. Org. Chem.

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“…To optimize the reaction conditions, the sulfinyl−lithium exchange was first examined with the fucosyl phenyl sulfoxide 1 quenching with CD 3 OD (Scheme 2). Compound 1 was prepared efficiently from l -fucose following a procedure described by us 12b. To prevent 1,2-elimination, the 2-hydroxyl must be deprotonated before anomeric lithiation.…”

Section: Resultsmentioning

confidence: 99%

Stereospecific Synthesis of α- and β-C-Glycosides from Glycosyl Sulfoxides: Scope and Limitations

Carpintero¹,

Nieto²,

Fernández-Mayoralas³

2001

J. Org. Chem.

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C-Glycosides derived from alpha-L-fuco-, alpha-D-gluco-, beta-D-gluco-, and alpha-D-mannopyranose have been synthesized from the corresponding glycosyl phenyl sulfoxide through phenylsulfinyl-lithium exchange, to generate an anomeric carbanion, and subsequent reaction with a carbon electrophile. The reactions were stereospecific and proceeded with retention of the configuration at the anomeric center. Improved yields of C-glycosides were obtained by an inverse addition protocol. Trapping of the anomeric carbanion with aldehydes gave best results. Reaction with ketones, chloroformates, nitriles, and alkyl halides was also explored. Mechanistic aspects of the reaction are discussed.

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“…C -Sialylation of thioglycoside 488 with aldehyde 489 promoted by SmI 2 gave α- C -linked disaccharide 490 in 93% yield (Scheme ). β- d -Glucosyl sulfoxide 491 was subjected to phenylsulfinyl lithium exchange to generate glycosyl lithium, which was reacted with isobutyraldehyde to give β- C -glycoside 492 in 50% yield with retention of the anomeric configuration. , The promoter system SmI 2 /NiI 2 has been reported to promote the C -glycosylation of glucosyl 2-pyridyl sulfone 493 with tert -butyl acrylate 494 , providing α- C -glycoside 495 in good yield (80%) . In addition, treatment of thioglycoside with lithium 4,4′-di- tert -butylbiphenylide (LiDBB) gave rise to glycosyl lithium, which was added to carbonyl compounds to afford the corresponding C -glycosides in good yields but with poor diastereoselectivities …”

Section: C-glycosylation With Thioglycosides Sulfoxides and Sulfonesmentioning

confidence: 99%

Recent Advances in the Chemical Synthesis of C-Glycosides

2017

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Advances in the chemical synthesis of C-pyranosides/furanosides are summarized, covering the literature from 2000 to 2016. The majority of the methods take advantage of the construction of the glycosidic C-C bond. These C-glycosylation methods are categorized herein in terms of the glycosyl donor precursors, which are commonly used in O-glycoside synthesis and are easily accessible to nonspecialists. They include glycosyl halides, glycals, sugar acetates, sugar lactols, sugar lactones, 1,2-anhydro sugars, thioglycosides/sulfoxides/sulfones, selenoglycosides/telluroglycosides, methyl glycosides, and glycosyl imidates/phosphates. Mechanistically, C-glycosylation reactions can involve glycosyl electrophilic/cationic species, anionic species, radical species, or transition-metal complexes, which are discussed as subcategories under each type of sugar precursor. Moreover, intramolecular rearrangements, such as the Claisen rearrangement, Ramberg-Bäcklund rearrangement, and 1,2-Wittig rearrangement, which usually involve concerted pathways, constitute another category of C-glycosylations. An alternative to the C-glycosylations is the formation of pyranoside/furanoside rings after construction of the predetermined glycosidic C-C bonds, which might involve cyclization of acyclic precursors or D-A cycloadditions. Throughout, the stereoselectivity in the formation of the resultant C-glycosidic linkages is highlighted.

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Stereoselective Synthesis ofcarba- andC-Glycosyl Analogs of Fucopyranosides

Cited by 31 publications

References 44 publications

Synthesis and Biological Evaluation of α-L-Fucosidase Inhibitors: 5a-Carba-α-L-fucopyranosylamine and Related Compounds

Synthesis and Biological Evaluation of α-L-Fucosidase Inhibitors: 5a-Carba-α-L-fucopyranosylamine and Related Compounds

Stereospecific Synthesis of α- and β-C-Glycosides from Glycosyl Sulfoxides: Scope and Limitations

Recent Advances in the Chemical Synthesis of C-Glycosides

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