3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-enopyranos-2-ulose | 211800-60-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-enopyranos-2-ulose
• 英文别名: 3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-en-2-ulopyranose；3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-en-2-ulose；(6S)-4-acetoxy-6-acetoxymethyl-2H-pyran-3(6H)-one；[(2S)-4-acetyloxy-5-oxo-2H-pyran-2-yl]methyl acetate
• CAS: 211800-60-1
• 化学式: C₁₀H₁₂O₆
• 分子量: 228.202
• InChiKey: MFJSVANWCIAHNG-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-enopyranos-2-ulose 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 1.5h， 以39%的产率得到3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-threo-hex-2-ulose
  参考文献：
  名称：

  1,5-Anhydro-D-Fructose: Stereoselective Conversions to 1,5-Anhydroalditols and Deoxy/Amino Substituted Analogues

  摘要：

  1,5-Anhydro-D-fructose (1) has been converted into crystalline oximes. 1,5-Anhydroalditols and 2-amino-2-deoxy-1,5-anhydroalditols have been prepared by stereoselective reduction procedures from 1 and from the oximes, respectively.

  DOI：

  10.1080/07328300008544112
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-1,5-anhydro-D-tagatose 在 sodium acetate 作用下， 以 丙酮 为溶剂， 反应 1.0h， 以91%的产率得到3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-enopyranos-2-ulose
  参考文献：
  名称：

  A convenient access to the 1,5-anhydro forms of d-tagatose, l-rhamnulose and d-xylulose via 2-hydroxyglycal esters

  摘要：

  Zemplen methanolysis or a three-step protocol comprising hydroxylaminolysis, de-O-acetylation and deoximination smoothly and efficiently convert the benzoylated 2-hydroxy-D-glycals Of D-galactose, L-rhamnose and D-Xylose into their configurationally related 1,5-anhydro-ketoses, thereby providing convenient access to the 1,5-anhydro forms of D-tagatose, L-rhamnulose and D-Xylulose. Invariably obtained as amorphous solids, they are best characterized through their highly crystalline oximes. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.03.016

文献信息

• A new chemical synthesis of Ascopyrone P from 1,5-anhydro-d-fructose
  作者：Mikkel Andreassen、Inge Lundt

  DOI：10.1016/j.carres.2006.03.037

  日期：2006.7

  The naturally occurring antioxidant Ascopyrone P (1,5-anhydro-4-deoxy-D-glycero-hex-1-en-3-ulose, 1) was prepared from the rare sugar 1,5-anhydroD-fructose (AF, 3) in three steps in an overall yield of 36%. Thus, acetylation of 3 afforded the enolone 3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-en-2-ulopyranose (4), which could be isomerised to 2,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-1-ene-3-ulose (6). Deacetylation of 6 under mild conditions gave crystalline Ascopyrone P (1). (c) 2006 Elsevier Ltd. All rights reserved.
• 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
  作者：Manfred Brehm、Volker H. Göckel、Pan Jarglis、Frieder W. Lichtenthaler

  DOI：10.1016/j.tetasy.2008.01.019

  日期：2008.2

  High-yielding protocols are described to convert D-glucose-via hydroxylaminolysis of its hydroxyglucal esters, followed by deoximination and beta-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. (C) 2008 Elsevier Ltd. All rights reserved.
• ASCOPYRONE P: CHEMICAL SYNTHESIS FROM d-GLUCOSE
  作者：S. Andersen、H. Jensen、S. Yu

  DOI：10.1081/car-120016855

  日期：——

  The pyranone, 1,5-anhydro-4-deoxy-D-glycero-hex-1-en-3-ulose (1) (ascopyrone P), has been synthesised in eight steps from D-glucose. The key steps were deacetylation of 3,6-di-O-acetyl-1,5-anhydro-D-glycero-hex-3-en-2-ulose (8) to give isomers and hydrates of 1,5-anhydro-4-deoxy-D-glycero-hex-3-en-2-ulose (9). Isomerisation of this mixture afforded 1,5-anhydro-4-deoxy-D-glycero-hex-1-en-3-ulose (1) (ascopyrone P) in a moderate yield.
• Synthesis and co-polymerization of an unsaturated 1,5-anhydro-d-fructose derivative
  作者：Olaf Deppe、Anke Glümer、Shukun Yu、Klaus Buchholz

  DOI：10.1016/j.carres.2004.06.007

  日期：2004.8

  An unsaturated derivative, 3,6-di-O-acetyl-1,5-anhydro-4-deoxy-D-glycero-hex-3-enopyranos-2-ulose (3), was obtained via regioselective elimination and acetylation of monohydrated 1, 5-anhydro-D-fructose (1) in a single step reaction. High yield (80%) was achieved without any dimeric by-products. Its co-polymerization to saccharide polymers was investigated with different commercial vinyl co-monomers. Co-polymers were obtained and characterized. (C) 2004 Elsevier Ltd. All rights reserved.
• Structure of 1,5-Anhydro-D-fructose: X-ray Analysis of Crystalline Acetylated Dimeric Forms
  作者：Søren M. Andersen、Inge Lundt、Jan Marcussen、I. Søtofte、Shukun Yu

  DOI：10.1080/07328309808001881

  日期：1998.9.1

  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.