2R,3S-2,3-O-cyclohexylidene-butan-1,2,3,4-tetrol | 141316-87-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2R,3S-2,3-O-cyclohexylidene-butan-1,2,3,4-tetrol
• 英文别名: 2,3-O-cyclohexylidene-erythritol；[(2R,3S)-3-(hydroxymethyl)-1,4-dioxaspiro[4.5]decan-2-yl]methanol
• CAS: 141316-87-2
• 化学式: C₁₀H₁₈O₄
• 分子量: 202.251
• InChiKey: ABVCJORPEQXLLH-DTORHVGOSA-N

物化性质

• 沸点：
  353.8±17.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2R,3S-2,3-O-cyclohexylidene-butan-1,2,3,4-tetrol 在 sodium hydroxide 、 phosphate buffer 作用下， 以 甲苯 为溶剂， 反应 15.0h， 生成 (2S,3R)-2,3-O-cyclohexylideneerythritol 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：

  (2R,3S)-2,3,4-三羟基-gamma-丁内酯2,3-环己基缩酮 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以86%的产率得到2R,3S-2,3-O-cyclohexylidene-butan-1,2,3,4-tetrol
  参考文献：
  名称：

  Cooperative attractive interactions in asymmetric hydrogenations with dihydroxydiphosphine Rh(I) catalysts — a competition study

  摘要：

  Studies for controlling rate and enantioselectivity of the asymmetric hydrogenation with Rh-diphosphine catalysts by cooperative attractive interactions within the framework of catalyst-substrate complexes are represented. In strong contrast to a Rh(I)[three-1,4-bis(diphenylphosphino)butane-2,3-diol] catalyst an extremely fast reaction took place applying the complex of the analogue erythro ligand. This is likely due to a strong intramolecular hydrogen bond between the vicinal HO groups impeding the hemilabile coordination of one of the hydroxy groups on the metal center during the hydrogenation. When a substrate with strong hydrogen bond acceptor properties such as (E)-methyl 3-dimethoxyphosphorylbut-2-enoate was hydrogenated even the three catalyst exhibited a fast reaction. The product was obtained in 83% ee. In contrast, when in the ligand both HO groups were replaced by MeO groups only poor conversion and 24% ee were achieved. While with the complex bearing HO groups in methanolic solution the corresponding diastereomeric catalyst substrate complexes were dominant, analogue MeO groups bearing catalyst substrate complexes could not be detected by NMR. For the latter, only the Rh(I)-solvent complex was found revealing the high importance of the additional functional groups on this equilibrium. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00071-1

文献信息

• Highly Diastereoselective Additions to Polyhydroxylated Pyrrolidine Cyclic Imines: Ready Elaboration of Aza-Sugar Scaffolds To Create Diverse Carbohydrate-Processing Enzyme Probes
  作者：Timothy M. Chapman、Steve Courtney、Phil Hay、Benjamin G. Davis

  DOI：10.1002/chem.200304718

  日期：2003.7.21

  and threitol polyhydroxylated pyrrolidine imine scaffolds have been rapidly elaborated to diversely functionalized aza-sugars through highly diastereoselective organometallic (RM) additions (R=Me, Et, allyl, hexenyl, Ph, Bn, pMeO-Bn). The yields for these additions have all been substantially enhanced from previously optimised levels (<58 %) for normal additions using a reverse addition procedure (e

  通过高度非对映选择性有机金属（RM）添加（R=Me、Et、烯丙基、己烯基、Ph、Bn、pMeO-Bn），代表性的非对映异构体、赤藓糖醇和苏糖醇多羟基化吡咯烷亚胺支架已被快速制备成多种功能化的氮杂糖。这些添加的产率均已从先前使用反向添加程序（例如 R=Ph；44% 正常模式 --> 78% 反向模式）的正常添加的优化水平（<58%）显着提高。高非对映选择性（除 R = Me 外，所有的均 > 98 % de）与受与偶氮甲亚胺碳相邻的 C-2 中心的构型和吡咯烷亚胺的构象控制的添加相一致。1-epi-和 2-epi-去乙酰茴香霉素的简明合成证明了该方法的高潜力。此外，这种亚胺添加方法允许在后期添加疏水性取代基，从而能够制备具有增强抑制潜力的新型氮杂糖。通过针对 12 种非哺乳动物和人类碳水化合物加工酶的不同小组筛选这些“疏水改性”氮杂糖的代表性选择来突出这一点。这确定了一种新型纳摩尔 α-半乳糖苷酶抑制剂
• Cooperative attractive interactions in asymmetric hydrogenations with dihydroxydiphosphine Rh(I) catalysts — a competition study
  作者：Jens Holz、Renat Kadyrov*、Susanne Borns、Detlef Heller、Armin Börner*

  DOI：10.1016/s0022-328x(00)00071-1

  日期：2000.5

  Studies for controlling rate and enantioselectivity of the asymmetric hydrogenation with Rh-diphosphine catalysts by cooperative attractive interactions within the framework of catalyst-substrate complexes are represented. In strong contrast to a Rh(I)[three-1,4-bis(diphenylphosphino)butane-2,3-diol] catalyst an extremely fast reaction took place applying the complex of the analogue erythro ligand. This is likely due to a strong intramolecular hydrogen bond between the vicinal HO groups impeding the hemilabile coordination of one of the hydroxy groups on the metal center during the hydrogenation. When a substrate with strong hydrogen bond acceptor properties such as (E)-methyl 3-dimethoxyphosphorylbut-2-enoate was hydrogenated even the three catalyst exhibited a fast reaction. The product was obtained in 83% ee. In contrast, when in the ligand both HO groups were replaced by MeO groups only poor conversion and 24% ee were achieved. While with the complex bearing HO groups in methanolic solution the corresponding diastereomeric catalyst substrate complexes were dominant, analogue MeO groups bearing catalyst substrate complexes could not be detected by NMR. For the latter, only the Rh(I)-solvent complex was found revealing the high importance of the additional functional groups on this equilibrium. (C) 2000 Elsevier Science S.A. All rights reserved.
• 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%。