3,5-Dinitrobenzoic acid catalyzed synthesis of 2,3-unsaturated O- and S-glycosides and tetrahydropyranylation of alcohols and phenols

Bodipati, Naganjaneyulu; Palla, Srinivasa Rao; Komera, Venkateshwarlu; Peddinti, Rama Krishna

doi:10.1016/j.tetlet.2014.10.093

Cited by 8 publications

(5 citation statements)

References 51 publications

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“…[1927-68-0]: Using the general procedure for etherification described above, peroxide 14b (101 mg, 0.50 mmol) was reacted with n -BuLi (0.31 mL 1.6 M in hexane, 0.5 mmol) to furnish ether 17h (12 mg, 15%) accompanied by 16 mg (15%) of recovered 14b . Partial spectral characterization has been reported …”

Section: Methodssupporting

confidence: 87%

“…Partial spectral characterization has been reported. 73 R f = 0.5 (15% EA/Hex); 1 H NMR: 4.59 (m, 1H), 3.89 (m, 1H), 3.76 (m, 1H), 3.52 (m, 1H), 3.40 (m, 1H), 1.84 (m, 1H), 1.72 (m, 1H), 1.65–1.49 (m, 6H), 1.45–1.35 (m, 2H), 0.94 (t, J = 7.3 Hz, 3H); 13 C NMR: 98.8, 67.3, 62.3, 31.8, 30.8, 25.5, 19.7, 1.4, 13.9.…”

Section: Methodsmentioning

confidence: 99%

“…Partial spectral characterization has been reported. 73 2-Hexyloxy-tetrahydro-2H-pyran (17i). [1927-63-5] Using the general procedure for etherification with alkyl magnesium bromide described above, peroxide 14b (107 mg, 0.5 mmol) was reacted with n-hexyl magnesium bromide (0.25 mL, 2 M in diethyl ether, 0.50 mmol) to furnish hexyl ether 17i as a colorless oil (57 mg, 61%).…”

Section: -Hexyloxy Octane (17g)mentioning

confidence: 99%

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Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

et al. 2015

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Although transfer of electrophilic alkoxyl (“RO+”) from organic peroxides to organometallics offers a complement to traditional methods for etherification, application has been limited by constraints associated with peroxide reactivity and stability. We now demonstrate that readily prepared tetrahydropyranyl monoperoxyacetals react with sp3 and sp2 organolithium and organomagnesium reagents to furnish moderate to high yields of ethers. The method is successfully applied to the synthesis of alkyl, alkenyl, aryl, heteroaryl, and cyclopropyl ethers, mixed O,O-acetals, and S,S,O-orthoesters. In contrast to reactions of dialkyl and alkyl/silyl peroxides, the displacements of monoperoxyacetals provide no evidence for alkoxy radical intermediates. At the same time, the high yields observed for transfer of primary, secondary, or tertiary alkoxides, the latter involving attack on neopentyl oxygen, are inconsistent with an SN2 mechanism. Theoretical studies suggest a mechanism involving Lewis acid promoted insertion of organometallics into the O–O bond.

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Section: Methodssupporting

confidence: 87%

Section: Methodsmentioning

confidence: 99%

Section: -Hexyloxy Octane (17g)mentioning

confidence: 99%

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Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

et al. 2015

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“…Various other catalyst systems have been developed over the decade, promoting the formation of 2,3‐unsaturated O‐ and C‐glycosides from glycals. Notable ones are cyanuric chloride‐catalyzed Ferrier reaction, bromodimethylsulfonium (BDMS)‐mediated rearrangement, and 3,5‐dinitrobenzoic acid (DNBA)‐mediated synthesis of O and S‐glycoside . The incorporation of potassium alkynyltrifluoroborate group to the glucal has also been implemented by BF 3 ⋅Et 2 O‐mediated Ferrier glycosidation.…”

Section: Glycosylationsmentioning

confidence: 99%

Chemical O‐Glycosylations: An Overview

2016

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The development of glycobiology relies on the sources of particular oligosaccharides in their purest forms. As the isolation of the oligosaccharide structures from natural sources is not a reliable option for providing samples with homogeneity, chemical means become pertinent. The growing demand for diverse oligosaccharide structures has prompted the advancement of chemical strategies to stitch sugar molecules with precise stereo‐ and regioselectivity through the formation of glycosidic bonds. This Review will focus on the key developments towards chemical O‐glycosylations in the current century. Synthesis of novel glycosyl donors and acceptors and their unique activation for successful glycosylation are discussed. This Review concludes with a summary of recent developments and comments on future prospects.

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“…Various methods of thioglycoside synthesis have mainly focused on two aspects: ionic and radical reactions (Figure B). Although ionic reactions have been developed for many years, they generate a mixture of α/β anomers in most cases. − Because of the efficient stereoselectivity of anomeric radicals, − chemists have developed a series of radical reactions to construct thioglycosides to compensate for the defects of ionic reactions. ,, Since the first glycosylation reaction of glycal donor was reported in 1964, building a stereoselective glycosideis a persistent aim with diverse biological and pharmaceutical goals. − Although axial glycosides can be obtained via anomeric effects, they are indispensable for stoichiometric Lewis − or Brønsted , acids, dramatically restricting the functional group compatibility. Equatorial glycosides can be generated via the gauche effect, limited to a structure by ortho-hydroxyl groups protected with acyl groups.…”

mentioning

confidence: 99%

Diastereoselective Synthesis of Thioglycosides via Pd-Catalyzed Allylic Rearrangement

Wang

Jiang

2021

Org. Lett.

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Stereoselective glycosylation is challenging in carbohydrate chemistry. Herein, stereoselective thioglycosylation of glycals via palladium-catalyzed allylic rearrangement yields various substituents on α-isomer thioglycosides. Two comprehensive series of aryl and benzyl thioglycosides were obtained via a combination of thiosulfates with glycals derived from glucose, arabinose, galactose, and rhamnose. Furthermore, diosgenyl α-l-rhamnoside and isoquercitrin achieved selectivity via stereospecific [2,3]-sigma rearrangements of α-sulfoxide-rhamnoside and α-sulfoxide-glucoside, respectively. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.1c03302. Descriptions of experimental procedures for compounds and analytical characterization (PDF)Accession Codes

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3,5-Dinitrobenzoic acid catalyzed synthesis of 2,3-unsaturated O- and S-glycosides and tetrahydropyranylation of alcohols and phenols

Cited by 8 publications

References 51 publications

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

Synthesis of Ethers via Reaction of Carbanions and Monoperoxyacetals

Chemical O‐Glycosylations: An Overview

Diastereoselective Synthesis of Thioglycosides via Pd-Catalyzed Allylic Rearrangement

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