(1R,2S,3S,4S,5R,6S)-1,6-isopropylidenedioxy-2,3-epoxycyclohexane-4,5-diol | 130669-73-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1R,2S,3S,4S,5R,6S)-1,6-isopropylidenedioxy-2,3-epoxycyclohexane-4,5-diol
• 英文别名: (1S,2R,3R,4S,5R,6S)-2,3-dihydroxy-4,5-di-O-isopropylidene-7-oxabicyclo<4.1.0>heptane；(1R,2S,3S,4S,5R,6S)-4,5-Dihydroxy-1,6-di-O-isopropylidene-2,3-epoxycyclohexane；(1R,2S,4S,5S,6R,7S)-9,9-dimethyl-3,8,10-trioxatricyclo[5.3.0.02,4]decane-5,6-diol
• CAS: 130669-73-7
• 化学式: C₉H₁₄O₅
• 分子量: 202.207
• InChiKey: XGNLUOKMXFGWEF-ZDJZFTHGSA-N

物化性质

• 沸点：
  360.7±42.0 °C(Predicted)
• 密度：
  1.394±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  71.4
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1R,2S,3S,4S,5R,6S)-1,6-isopropylidenedioxy-2,3-epoxycyclohexane-4,5-diol 在 sodium benzoate 作用下， 以 水 为溶剂， 反应 83.0h， 以77%的产率得到肌糖
  参考文献：
  名称：

  Unusual oxidation of 1-halo-1,3-dienes with parmanganate. Expedient syntheses of (+)-D-chiro-3-inosose and (+)-D-chiro-inositol from chlorobenzene

  摘要：

  DOI：

  10.1021/jo00060a061
• 作为产物：
  描述：

  [3aS-(3aα,4α,5α,7aα)]-3a,4,5,7a-四氢-2,2-二甲基-1,3-苯并间二氧杂环戊烯-4,5-二醇 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以88%的产率得到(1R,2S,3S,4S,5R,6S)-1,6-isopropylidenedioxy-2,3-epoxycyclohexane-4,5-diol
  参考文献：
  名称：

  Hudlicky, Tomas; Rulin, Fan; Tsunoda, Toshiya, Israel Journal of Chemistry, 1991, vol. 31, # 3, p. 229 - 238

  摘要：

  DOI：

文献信息

• Ring-opening of hindered cyclic epoxides with potassium carboxylates in the presence of conjugate acids
  作者：John F. Trant、Tomas Hudlicky

  DOI：10.1139/cjc-2013-0386

  日期：2013.12

  During attempts to ring-open a highly hindered epoxide, traditional methods were found to be ineffective. An alternative strategy for opening epoxides was implemented that employed a potassium carboxylate in the presence of its conjugate acid in a solvent mixture containing polar and potassium-sequestering components. A systematic analysis of the components of the reaction mixture indicated that the addition of the conjugate acid was the most important feature for providing good conversion. This reaction appears to be general for most classes of carboxylic acids including cinnamic, aromatic, and highly hindered carboxylic acids (30%–79% yield) and only fails with weak carboxylate nucleophiles. Three highly substituted and hindered cyclohexene oxide derivatives were examined for reactivity and the reaction conditions appear to tolerate a variety of functional groups to provide the ring-opened species. This pH-moderate system proved useful for hindered cyclic epoxides when all other techniques failed and should prove general to a wide spectrum of epoxide and carboxylic acid partners in those cases where the use of a strong Lewis or protic acid catalyst, or a strong basic nucleophile, is inappropriate.

  在尝试开环一个高度阻碍的环氧化物时，发现传统方法无效。实施了一种替代策略来打开环氧化物，该策略利用了存在其共轭酸的钾羧酸盐，在含有极性和钾离子螯合成分的溶剂混合物中。对反应混合物组分的系统分析表明，添加共轭酸是提供良好转化的最重要特征。这种反应似乎适用于大多数类别的羧酸，包括肉桂酸、芳香族和高度阻碍的羧酸（30%–79% 收率），只有对弱羧酸亲核试剂失败。对三种高度取代和阻碍的环己烯氧化物衍生物进行了反应性检验，反应条件似乎能容忍各种官能团以提供开环物种。这种pH适中的体系在所有其他技术失败时对阻碍的环氧化物非常有用，并且在不适合使用强Lewis酸或质子酸催化剂，或强碱亲核试剂的情况下，应该适用于广泛的环氧化物和羧酸配体。
• General synthesis of inositols by hydrolysis of conduritol epoxides obtained biocatalytically from halogenobenzenes: (+)-D-chiro-inositol, allo-inositol, muco-inositol and neo-inositol
  作者：Martin Mandel、Tomas Hudlicky

  DOI：10.1039/p19930000741

  日期：——

  Four of the nine isomeric inositols have been prepared by hydrolytic opening of epoxides derived from 3-halogenocyclohexa-3,5-diene-1,2-diol by further oxidation with potassium permanganate or by reduction of chiro-3-inosose (2L-2,3,6/4,5-pentahydroxycyclohexanone).

  九个异构体肌醇的四个已制备通过用高锰酸钾通过进一步氧化由3- halogenocyclohexa -3,5-二烯-1,2-二醇衍生的环氧化物的水解或开口通过还原的手性-3-肌糖（2大号- 2,3,6 / 4,5-五羟基环己酮）。
• Chemoenzymatic enantiodivergent synthesis of 1,2-dideoxy-2-amino-1-fluoro-allo-inositol
  作者：Kofi A. Oppong、Tomas Hudlicky、Fengyang Yan、Chentao York、Ba V. Nguyen

  DOI：10.1016/s0040-4020(99)00080-0

  日期：1999.3

  Both enantiomers of dideoxyfluoroamino inositols (+)-9 and (-)-9 were synthesized from bromocyclohexadiene cis-diol 1 obtained by microbial oxidation of bromobenzene with toluene dioxygenase. Selective introduction of the amino group was achieved through S(N)2 displacement of triflates 7, 11. Fluorine was selectively introduced via trans-diaxial epoxide opening with tetrabutylphosphonium fluoride dihydrofluoride (TBPF-DF). (C) 1999 Elsevier Science Ltd. All rights reserved.
• Intermediate for the synthesis of D-chiro-3-inosose and (+)-D-chiro-inositol
  申请人：VIRGINIA TECH INTELLECTUAL PROPERTIES, INC.

  公开号：EP1225175B1

  公开（公告）日：2005-03-30
• Synthesis of chiral ADMET polymers containing repeating d-chiro-inositol units derived from a biocatalytically prepared diene diol
  作者：Vu P Bui、Tomas Hudlicky

  DOI：10.1016/j.tet.2003.10.097

  日期：2004.1

  Several chiral hydroxylated polymers have been prepared, via ADMET techniques, from the diene diol derived from bromobenzene, obtained by means of whole-cell fermentation with Escherichia coli (JM109 pDTG601). (C) 2003 Elsevier Ltd. All rights reserved.