75414-38-9

Upstream product

• 75414-32-3 1,5-anhydro-3,4,6-tri-O-benzoyl-D-fructose 
• 75414-43-6 1,5-D-anhydrofructose 
• 98-88-4 benzoyl chloride 
• 82569-81-1 1,5-anhydro-3,4,6-tri-O-benzoyl-D-fructose oxime 
• 75414-21-0 3,4,6-tri-O-benzoyl-1,5-anhydro-D-fructose E-oxime 
• 14125-75-8 2,3,4,6-tetra-O-benzoyl-D-hydroxyglucal 

Downstream Products

• 111718-41-3 (2S,5S)-5-benzoyloxy-2-benzoyloxymethyl-5-methyltetrahydropyran-4-one 
• 111718-42-4 (2S,5S)-5-allyl-5-benzoyloxy-2-benzoyloxymethyltetrahydropyran-4-one 
• 111718-43-5 C₂₄H₂₄O₆ 
• 111718-43-5 C₂₄H₂₄O₆ 
• 33886-26-9 5-Benzoyloxy-2-benzoyloxymethyl-4H-pyran-4-on 
• 75414-41-4 (6S)-4-benzoyloxy-6-benzoyloxymethyl-2H-pyran-3(6H)-one 
• 111718-45-7 C₂₅H₂₂O₆ 
• 111718-45-7 C₂₅H₂₂O₆ 
• 111718-46-8 3,6-di-O-benzoyl-4-deoxy-4-C-methyl-1,5-anhydro-D-frucrose 
• 1017969-07-1 (2S)-2-benzoyloxymethyl-5,5-bis(nitromethyl)tetrahydropyran-4-one 
• 1017969-01-5 (6S)-6-benzoyloxymethyl-3,3-dimethoxytetrahydropyran-4-one 
• 1017969-06-0 (2S,4S,5R)-5-benzoyloxy-2-benzoyloxymethyl-4-hydroxytetrahydropyran 
• 1017969-05-9 (3S)-3-benzoyloxymethyl-3,4-dihydro-1H-pyrano[3,4-b]quinoxaline 
• 1017969-03-7 (6S)-4-benzoyloxy-6-benzoyloxymethyl-2H-pyran-3(6H)-one phenylhydrazone 

Relevant academic research and scientific papers

Expedient conversion of d-glucose into 1,5-anhydro-d-fructose and into single stereogenic-center dihydropyranones, suitable six-carbon scaffolds for concise syntheses of the soft-coral constituents (-)-bissetone and (-)-palythazine

High-yielding protocols are described to convert d-glucose-via hydroxylaminolysis of its hydroxyglucal esters, followed by deoximination and β-elimination of acid-into dihydropyranone building blocks with a single stereogenic center. Their versatility as enantiopure six-carbon scaffolds is highlighted by excellent regio- and stereocontrol in a variety of addition reactions and by their straightforward use as building blocks for the concise syntheses of the soft-coral constituents bissetone and palythazine in enantiopure form, thereby proving their absolute configuration. Moreover, several procedures are detailed to convert hydroxyglucal esters into 1,5-anhydro-d-fructose, their parent sugar, the direct low-temperature de-O-acylation being the most suitable for preparative purposes, as long as its access via enzymatic degradation of starch is not implemented on an appreciable scale.

Structure of 1,5-anhydro-D-fructose: X-ray analysis of crystalline acetylated dimeric forms

Acetylation of 1,5-anhydro-D-fructose under acidic conditions gave two crystalline acetylated dimeric forms, which by X-ray analysis were shown to be diastereomeric spiroketals formed between C-2 and C-2/C-3. The structures of the compounds differed only at the configuration at C-2. Acetylation or benzoylation of 1,5-anhydro-D-fructose in pyridine yielded 3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-enos-2-ulopyra-nose or crystalline 1,5-anhydro-3,6-di-O-benzoyl-4-deoxy-D-glycero-hex-3-enos-2-ulo-pyranose.

A CONVENIENT ACCESS TO 1,5-ANHYDROKETOSES

A convenient, verstile entry into the 1,5-anhydroketose series is described and their conversion into enolones, enolone oximes and γ-pyrones.