1,4-diacetyl-2,3-O-isopropylidene-meso-erythrol | 124867-21-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,4-diacetyl-2,3-O-isopropylidene-meso-erythrol
• 英文别名: 2,3-O-isopropylideneerythritol diacetate；[(4R,5S)-5-(acetyloxymethyl)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl acetate
• CAS: 124867-21-6
• 化学式: C₁₁H₁₈O₆
• 分子量: 246.26
• InChiKey: BDOLBKCDFFBHCQ-AOOOYVTPSA-N

物化性质

• 沸点：
  301.0±27.0 °C(Predicted)
• 密度：
  1.097±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.63
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1,4-diacetyl-2,3-O-isopropylidene-meso-erythrol 在 sodium hydroxide 、 phosphate buffer 作用下， 反应 15.0h， 以70%的产率得到2,3-O-isopropylideneerythritol monoacetate
  参考文献：
  名称：

  Enzyme-Catalyzed Asymmetric Synthesis; 10.¹ Pseudomonas cepaciaLipase Mediated Synthesis of Enantiomerically Pure (2R,3S)- and (2S,3R)-2,3-O-Cyclohexylideneerythritol Monoacetate from 2,3-O-Cyclohexylideneerythritol

  摘要：

  在水和二异丙基醚乳液中，假单胞菌脂肪酶催化 2，3-O-环己亚基季戊四醇二乙酸酯水解，得到 (2S,3R)-2.O-环己亚基季戊四醇单乙酸酯[(2S,3R)-1-乙酰氧基-2,3-环己亚基二氧-4-羟基双酚]、 (2S,3R)-2,3-O-环己亚基季戊四醇单乙酸酯[(2S,3R)-1-乙酰氧基-2,3-环己亚基二氧-4-羟基丁烷]，通过优先攻击 R 中心 CH2OAc 基团，ee ≥ 99%，收率 91%。在同一酶的催化下，用乙酸乙烯酯对 2,3-O-环己基亚赤藓醇进行乙酰化，可得到对映体（2R, 3S）-2,3-O-环己基亚赤藓醇单乙酸酯，通过在 R 中心 CH2OH 基团上的优先反应进行对映体和对映体分化，ee 值≥ 99%，收率为 78%。

  DOI：

  10.1055/s-1992-34187
• 作为产物：
  描述：

  dimethyl meso-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 在 吡啶 、 lithium aluminium tetrahydride 作用下， 生成 1,4-diacetyl-2,3-O-isopropylidene-meso-erythrol
  参考文献：
  名称：

  Preparation of a chiral building block based on 1,3-syn-diol using Pseudomonas fluorescens lipase and its application to the synthesis of a hunger modulator.

  摘要：

  通过使用荧光假单胞菌酯酶（PFL）对内消旋二乙酸酯（8）进行高度对映选择性水解，获得了一种新型手性构建单元（9），其由1,3-顺式二醇组成。利用（-）-9合成了具有调节饥饿活性之一的2-羟基-4-羟甲基-4-丁内酯的四种可能立体异构体之一。

  DOI：

  10.1248/cpb.37.1650

文献信息

• Synthesis of higher-carbon sugars via cross-aldolization of 7-oxanorbornan-2-one and carbohydrate aldehyde derivatives
  作者：Suruliappa Jeganathan、Pierre Vogel

  DOI：10.1039/c39890000993

  日期：——

  The TiCl4-induced condensation of (+)-(1S,4S,5S,6S)-5,6-isopropylidenedioxy-2-t-butyldimethylsilyloxy-7-oxabicyclo[2.2.1]hept-2-ene with 2,3-O-isopropylidene-D-glyceraldehyde was highly stereoselective, giving a product that was converted with high stereoselectivity into protected D-erythro-D-talo-octose and D-erthro-L-allo-octose.

  TiCl 4诱导的（+）-（1 S，4 S，5 S，6 S）-5,6-异丙基二烯二氧基-2-叔丁基二甲基甲硅烷氧基-7-氧杂双环[2.2.1]庚-2-烯的缩合与2,3- ö异亚丙基d甘油醛是高度立体选择性，从而，将其转变高立体选择性成保护的产品d -赤- d -距骨-octose和d - erthro -大号-异体-octose。
• Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. XII. Highly stereoselective total syntheses of octoses and derivatives
  作者：Suruliappa Jeganathan、Pierre Vogel

  DOI：10.1021/jo00003a041

  日期：1991.2

  Mukaiyama cross aldolizations of (R)-2,3-O-isopropylideneglyceraldehyde (10) with (1R,4S,5R,6R)-5-exo, 6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-8) were highly diastereoselective and led to the corresponding u,u,l or SYNCAT ((+)-11) and u,u,u or ANCAT ((-)-21) aldols, respectively. The results were interpreted in terms of extended open transition state models with (ul,lk) and (ul,ul) topicities, respectively, which minimize steric repulsions. Aldols (+)-11 and (-)-21 were converted into (tert-butyl)dimethylsilyl 6-O-acetyl-2,3:7, 8-di-O-isopropylidene-D-glycero-L-talo-alpha-octofuranosid-5-ulose ((-)-18) and its D-talo diastereomer ((+)-28), respectively. Reduction of (-)-18 with LiEt3BH in THF gave, after deprotection, the known D-threo-L-talo-octose ((-)-4). Reduction of (-)-18 with (i-Bu)2AlH/THF gave, after deprotection, the unknown D-threo-D-allo-octose ((+)-5) with high stereoselectivity. Similarly, the unknown D-erythro-D-talo-octose ((+)-6) and D-erythro-L-allo-octose ((-)-7) were derived from (+)-28 through reduction with LiB(s-Bu)3H and (i-Bu)2AlH, respectively.
• JEGANATHAN, SURULIAPPA;VOGEL, PIERRE, J. CHEM. SOC. CHEM. COMMUN.,(1989) N5, C. 993-995
  作者：JEGANATHAN, SURULIAPPA、VOGEL, PIERRE

  DOI：——

  日期：——
• Preparation of a chiral building block based on 1,3-syn-diol using Pseudomonas fluorescens lipase and its application to the synthesis of a hunger modulator.
  作者：Zhuo-Feng XIE、Kiyoshi SASAKI

  DOI：10.1248/cpb.37.1650

  日期：——

  A novel, chiral building block (9) consisting of 1, 3-syn-diol was obtained by highly enantioselective hydrolysis of the meso-diacetate (8) with Pseudomonas fluorescens lipase (PFL), and (-)-9 was used to synthesize one of four possible stereoisomers of 2-hydroxy-4-hydroxymethyl-4-butanolide, which has hunger modulating activities.

  通过使用荧光假单胞菌酯酶（PFL）对内消旋二乙酸酯（8）进行高度对映选择性水解，获得了一种新型手性构建单元（9），其由1,3-顺式二醇组成。利用（-）-9合成了具有调节饥饿活性之一的2-羟基-4-羟甲基-4-丁内酯的四种可能立体异构体之一。
• Enzyme-Catalyzed Asymmetric Synthesis; 10.¹ <i>Pseudomonas cepacia</i>Lipase Mediated Synthesis of Enantiomerically Pure (2<i>R</i>,3<i>S</i>)- and (2<i>S</i>,3<i>R</i>)-2,3-<i>O</i>-Cyclohexylideneerythritol Monoacetate from 2,3-<i>O</i>-Cyclohexylideneerythritol
  作者：Hans-Joachim Gais、Horst Hemmerle、Sebastian Kossek

  DOI：10.1055/s-1992-34187

  日期：——

  Pseudomonas cepacia lipase catalyzed hydrolysis of 2, 3-O-cyclohexylideneerythritol diacetate in an emulsion of water and diisopropyl ether gives (2S,3R)-2, 3-O-cyclohexylideneerythritol monoacetate [(2S, 3R)-1-acetoxy-2,3-cyclohexylidenedioxy-4-hydroxybutane] with ≥ 99% ee in 91% yield by a preferential attack at the R-center CH2OAc group. The enantiomeric (2R, 3S)-2,3-O-cyclohexylideneerythritol monoacetate is obtained by acetylation of 2,3-O-cyclohexylideneerythritol with vinyl acetate catalyzed by the same enzyme with ≥ 99% ee in 78% yield by a combined enantiotopos and enantiomer differentiation through a preferential attack at the R-center CH2OH groups.

  在水和二异丙基醚乳液中，假单胞菌脂肪酶催化 2，3-O-环己亚基季戊四醇二乙酸酯水解，得到 (2S,3R)-2.O-环己亚基季戊四醇单乙酸酯[(2S,3R)-1-乙酰氧基-2,3-环己亚基二氧-4-羟基双酚]、 (2S,3R)-2,3-O-环己亚基季戊四醇单乙酸酯[(2S,3R)-1-乙酰氧基-2,3-环己亚基二氧-4-羟基丁烷]，通过优先攻击 R 中心 CH2OAc 基团，ee ≥ 99%，收率 91%。在同一酶的催化下，用乙酸乙烯酯对 2,3-O-环己基亚赤藓醇进行乙酰化，可得到对映体（2R, 3S）-2,3-O-环己基亚赤藓醇单乙酸酯，通过在 R 中心 CH2OH 基团上的优先反应进行对映体和对映体分化，ee 值≥ 99%，收率为 78%。