Syntheses of derivatives of p-aminophenyl 3-O-(3,6-dideoxy-α-d-arabino- and α-d-ribo-hexopyranosyl)-α-d-mannopyranosides by use of hydroxyglycal intermediates

Ekborg, Göran; Garegg, Per J.; Josephson, Staffan

doi:10.1016/s0008-6215(00)84325-6

Cited by 12 publications

(2 citation statements)

References 14 publications

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“…Interestingly, the reaction of anhydrous hydrogen fluoride with d-fructose, sucrose, or inulin leads among others to did-fructose anhydride I 8, a tricyclic molecule with 2 1,6,9-trioxaspiro [4.5]decane ring systems. 50,51 In the early 1980s, we developed a practical method for the conversion of the 2 literature-known d-glucose-derived 2-hydroxyglycal esters 9a 52,53 and 9b 54 into the corresponding ulosyl bromides 10a 55,56 and 10b. 57 We subsequently published 58 the glycosylation of 10a with the diol ethylene glycol to the bicyclic pyranodioxane (1,4,5-trioxa-cisdecaline) 11a.…”

Section: Synthesesmentioning

confidence: 99%

Stereoselective Synthesis of 1,6,9-Tri-oxaspiro[4.5]decanes From d-Glucose: Novel Structural Motifs of Spiroacetal Natural Products

Cuny

2020

Natural Product Communications

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Spiroacetals are the central structural core element of numerous natural products and are essential for their biological activity. A typical structural representative of a spiroacetal is the bicyclic 1,6-dioxaspiro[4.5]decane ring system. It represents the complete or partial structure of many biologically potent natural products such as the Paravespula pheromone 1, the antibiotic (+)-monensin A 2, the anticancer agent (−)-berkelic acid 3, the antimitotic ingredient spirastrellolide F, characterized after methylation as (+)-methyl ester 4, and the marine toxin (−)-calyculin A 5. In these compounds, the 1,6-dioxaspiro[4.5]decane ring system is found in either spiro ( R)-6 or ( S) - 6 configuration. The corresponding 1,6,9-trioxaspiro[4.5]decane framework ( S)-7 and ( R)-7 with opposite chirality at the spiro center due to an additional oxygen atom at position 9 in the pyran portion has so far not been found in living organisms or been synthesized. To close this gap and enable structure–activity relationship studies, potentially leading to novel antibiotics and selective anticancer agents, we have developed an efficient and stereocontrolled route to the ( R)- and ( S)-configurated 1,6,9-trioxaspiro[4.5]decane ring system leading to oxa analog motifs of the above natural products.

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Section: Synthesesmentioning

confidence: 99%

Stereoselective Synthesis of 1,6,9-Tri-oxaspiro[4.5]decanes From d-Glucose: Novel Structural Motifs of Spiroacetal Natural Products

Cuny

2020

Natural Product Communications

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“…Table ). Furthermore, both donors are fairly well accessible from d -glucose through the 6-deoxy-2-hydroxyglucal ester 168 (Scheme ): ulosyl bromide 27 can be obtained in five large-scale adaptable steps from d -glucose versus seven steps for its unsaturated chloro analogue 169 , with overall yields of 42% and 25%, respectively.…”

Section: Ulosyl Donor Approach To β-D-man and β-L-rha Linkagesmentioning

confidence: 99%

2-Oxoglycosyl (“Ulosyl”) and 2-Oximinoglycosyl Bromides: Versatile Donors for the Expedient Assembly of Oligosaccharides with β-d-Mannose, β-l-Rhamnose, N-Acetyl-β-d-mannosamine, and N-Acetyl-β-d-mannosaminuronic Acid Units

Lichtenthaler

2011

Chem. Rev.

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|Chem. Rev. 2011, 111, 5569-5609 Chemical Reviews REVIEW in 1900, 16 their 2-oxohexosyl ("ulosyl") analogues were not encountered until 73 years later, when Collins et al. 17 subjected the 2-O-unprotected hexosyl chlorides of D-glucose and D-galactose to a ruthenium tetroxide oxidation, e.g., 1 f 2 (Scheme 2). The somewhat intricate accessibility of 2 and its galacto analoguefive steps from the underlying sugar in modest overall yields (15À20%)-and their capricious obtention as gums, however, have not invited their utilization as glycosyl donors for the synthesis of oligosaccharides.Only the elaboration of a simple, preparatively satisfactory access to their bromo analogues, the glycosulosyl bromides, from any of the common sugars 14 and the establishment of suitable conditions for β-specific glycosidation and manno-selective reduction 9 prompted their comprehensive use as indirect glycosyl donors for the straightforward synthesis of oligosaccharides containing β-D-mannose units.Key intermediates for the efficient generation of glycos-2-ulosyl bromides are the 2-(acyloxy)glycals. In their ester-protected form, they are most readily accessible from any of the basic monoor disaccharides in a large-scale adaptabe three-step procedure comprising acylation, bromination, and elimination of hydrogen bromide, as exemplified for the D-glucose case in Scheme 3. As the first two of these steps can be combined into a one-pot operation, the overall yields are in the 70% range. 18

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A Concise and General Method for Doubly Attaching 2‐Ketosugars to Aglycon Diols: Synthesis of the Gomphosides and Spectinomycin

Lichtenthaler¹,

Cuny²,

Sakanaka³

2005

Angewandte Chemie

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Syntheses of derivatives of p-aminophenyl 3-O-(3,6-dideoxy-α-d-arabino- and α-d-ribo-hexopyranosyl)-α-d-mannopyranosides by use of hydroxyglycal intermediates

Cited by 12 publications

References 14 publications

Stereoselective Synthesis of 1,6,9-Tri-oxaspiro[4.5]decanes From d-Glucose: Novel Structural Motifs of Spiroacetal Natural Products

Stereoselective Synthesis of 1,6,9-Tri-oxaspiro[4.5]decanes From d-Glucose: Novel Structural Motifs of Spiroacetal Natural Products

2-Oxoglycosyl (“Ulosyl”) and 2-Oximinoglycosyl Bromides: Versatile Donors for the Expedient Assembly of Oligosaccharides with β-d-Mannose, β-l-Rhamnose, N-Acetyl-β-d-mannosamine, and N-Acetyl-β-d-mannosaminuronic Acid Units

A Concise and General Method for Doubly Attaching 2‐Ketosugars to Aglycon Diols: Synthesis of the Gomphosides and Spectinomycin

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