rac-(1R,4R,5R)-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: rac-(1R,4R,5R)-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol
• 英文别名: (+/-)-anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol；anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol；(1S,4S,5S)-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol
• 化学式: C₆H₈O₃
• 分子量: 128.128
• InChiKey: DRRIYZQOHCHRML-SRQIZXRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  rac-(1R,4R,5R)-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol 在 四氧化锇 、 N-甲基吲哚酮 、 Candida cylindracea lipase VII 、 氨 、 硫脲 作用下， 以 甲醇 为溶剂， 反应 38.0h， 生成 原栎醇
  参考文献：
  名称：

  Resolution of (±)-anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol via Candida cylindracea lipase: synthesis of (−)- and (+)-proto-quercitol

  摘要：

  Photooxygenation of cyclohexa-1,4-diene afforded anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide. The hydroperoxy endoperoxide was reduced with dimethylsulfide-titanium tetraisopropoxide to produce ()-anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol. The highly efficient enantioselective resolution of the racemic (+/-)-anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol was accomplished with Candida cylindracea lipase (CCL) to produce the enantiomerically enriched alcohol and the corresponding acetate: The cleavage of the peroxide linkage by thiourea followed by the oxidation of the double bond with OsO4 resulted in the formation of (-)-proto-quercitol and (+)-proto-quercitol, respectively. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.11.037
• 作为产物：
  描述：

  anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide 在 titanium(IV) isopropylate 、 二甲基硫 、 Candida cylindracea lipase VII 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 38.0h， 生成 rac-(1R,4R,5R)-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol
  参考文献：
  名称：

  Resolution of (±)-anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol via Candida cylindracea lipase: synthesis of (−)- and (+)-proto-quercitol

  摘要：

  Photooxygenation of cyclohexa-1,4-diene afforded anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide. The hydroperoxy endoperoxide was reduced with dimethylsulfide-titanium tetraisopropoxide to produce ()-anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol. The highly efficient enantioselective resolution of the racemic (+/-)-anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol was accomplished with Candida cylindracea lipase (CCL) to produce the enantiomerically enriched alcohol and the corresponding acetate: The cleavage of the peroxide linkage by thiourea followed by the oxidation of the double bond with OsO4 resulted in the formation of (-)-proto-quercitol and (+)-proto-quercitol, respectively. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.11.037

文献信息

• A novel and short synthesis of (1,4/2)-cyclohex-5-ene-triol and its conversion to (±)-proto-quercitol
  作者：M.Serdar Gültekin、Emine Salamci、Metin Balci

  DOI：10.1016/s0008-6215(03)00256-8

  日期：2003.7

  (1,4/2)-Cyclohex-5-ene-triol was synthesized starting from cyclohexa-1,4-diene with two different approaches. Photooxygenation of cyclohexa-1,4-diene and epoxy-cyclohexene afforded anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide and anti-7-oxabicclo[4.1.0]hept-4-en-3-yl hydroperoxide, respectively. Hydroperoxy endoperoxide was reduced with aqueous sodium bisulfite; hydroperoxy-epoxide with dimethylsulfide-titanium tetraisopropoxide to give 7-oxabicyclo[4.1.0]hept-4-en-3-ol. Acidic hydrolysis of the epoxy-alcohol gave the (1,4/2)-cyclohex-3-ene-triol. Oxidation of the double bond with KMnO4 resulted in the formation of proto-quercitol. (C) 2003 Elsevier Ltd. All rights reserved.

  从环己-1,4-二烯出发，通过两种不同的方法合成了(1,4/2)-环己-5-烯三醇。环己-1,4-二烯和环氧环己烯的光氧反应分别生成了反式2,3-二氧双环[2.2.2]辛-7-烯-5-基过氧化氢和反式7-氧双环[4.1.0]庚-4-烯-3-基过氧化氢。水合亚硫酸钠将羟基过氧内过氧化物还原；二甲基亚砜-四异丙氧基钛将羟基过氧环氧物还原，得到7-氧双环[4.1.0]庚-4-烯-3-醇。环氧醇的酸性水解生成了(1,4/2)-环己-3-烯三醇。高锰酸钾氧化双键，生成了果糖苷二醇。©2003 Elsevier Ltd. 保留所有权利。
• Stereospecific synthesis of a dl-gala-aminoquercitol derivative
  作者：Namudar I. Kurbanoğlu、Murat Çelik、Hamdullah Kilic、Cemalettin Alp、Ertan Şahin、Metin Balci

  DOI：10.1016/j.tet.2010.03.028

  日期：2010.5

  A new aminoquercitol derivative was synthesized starting from 1,4-cyclohexadiene. Photooxygenation of cyclohexa-1,4-diene afforded anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxicle as the main product. The formed hydroperoxy endoperoxide was reduced with LiAlH(4) to produce anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-ol. Protection of alcohol with acetyl chloride followed by reduction of the endoperoxide with thiourea, and then palladium-catalyzed ionization/cyclization reaction gave an oxazolidinone derivative. Hydrolysis of the oxazolidinone ring and acetylation gave an amino compound. Oxidation of the double bond in the amino compound with OsO(4) followed by acetylation gave the amino tetraacetate and removal of the acetate groups furnished the desired aminoquercitol whose exact configuration was determined by X-ray diffraction analysis. (C) 2010 Elsevier Ltd. All rights reserved.