(+/-)-(1S*,2S*,6S*,7R*)-1,7,8,9-tetrachloro-10,10-dimethoxytricyclo[5.2.1.0^2,6]dec-8-en-3-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-(1S*,2S*,6S*,7R*)-1,7,8,9-tetrachloro-10,10-dimethoxytricyclo[5.2.1.0^2,6]dec-8-en-3-one
• 英文别名: (1S,2S,6S,7R)-1,7,8,9-tetrachloro-10,10-dimethoxytricyclo[5.2.1.02,6]dec-8-en-3-one
• 化学式: C₁₂H₁₂Cl₄O₃
• 分子量: 346.037
• InChiKey: ITONVGRJOJCRAF-UGFAFLPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-(1S*,2S*,6S*,7R*)-1,7,8,9-tetrachloro-10,10-dimethoxytricyclo[5.2.1.0^2,6]dec-8-en-3-one 在 盐酸 、 六甲基磷酰三胺 、 sodium tetrahydroborate 、 sodium 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醚 为溶剂， 反应 27.0h， 生成 (1S,2S,6S,7R,8S)-methyl 7-hydroxy-8-methyl-4-oxobicyclo[4.3.0]non-2-yl-carboxylate
  参考文献：
  名称：

  Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 1: EPC-synthesis of the hydrindene subunit of the cochleamycins

  摘要：

  A racemic as well as an EPC-synthesis of the cis-hydrindene subunit of the cochleamycins, physiologically active microbial secondary metabolites, are reported. The five stereogenic centres of this subunit are introduced in high stereoselectivity in a short sequence by intermolecular Diels-Alder reaction, stereoselective methylation and hydride reduction. Cyclisation via nucleophilic addition, acidic fragmentation, regioselective Shapiro reaction and inversion of a secondary alcohol are the further key steps of these syntheses. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.05.092
• 作为产物：
  描述：

  5,5-二甲氧基-1,2,3,4-四氯环戊二烯 在 palladium on activated charcoal jones' reagent 、 4 A molecular sieve 、 四丁基氟化铵 、 氢气 、 对苯二酚 作用下， 以 四氢呋喃 、 甲醇 、 溶剂黄146 、 丙酮 、 xylene 为溶剂， 115.0 ℃ 、101.33 kPa 条件下， 反应 146.5h， 生成 (+/-)-(1S*,2S*,6S*,7R*)-1,7,8,9-tetrachloro-10,10-dimethoxytricyclo[5.2.1.0^2,6]dec-8-en-3-one
  参考文献：
  名称：

  Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 2: EPC-synthesis of the hydrindene subunit of the macquarimicins

  摘要：

  The EPC-synthesis of the cis- hydrindene subunit of the macquarimicins, antibiotics with antitumour and anti-inflammatory activity, has been achieved. Desymmetrization of cis-1,4-cyclopent-2-enediol was succeeded by Diels-Alder reaction and functional group transformations to a tricyclic ketone. Regio- and stereoselective methylation via Claisen condensation and hydrogenation was followed by nucleophilic, intramolecular addition, reduction and acidic fragmentation. Further functional group transformations led to the target molecule. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.05.094

文献信息

• A versatile regio- and stereospecific annulation method - I
  作者：Edda Gössinger、Renate Müller

  DOI：10.1016/0040-4020(89)80136-x

  日期：1989.1
• Base-promoted eliminative cyclization: Novel synthesis of functionalized tetracyclo[6.2.1.02,7.04,10]Undecane and tetracyclo[5.3.0.02,6.05,9]Decane systems
  作者：Chandler Suri Suresh

  DOI：10.1016/s0040-4039(00)97447-1

  日期：——
• Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 1: EPC-synthesis of the hydrindene subunit of the cochleamycins
  作者：A. Chrobok、E. Gössinger、E. Orglmeister、K. Pflugseder、J. Schwaiger、F. Wuggenig

  DOI：10.1016/j.tet.2007.05.092

  日期：2007.8

  A racemic as well as an EPC-synthesis of the cis-hydrindene subunit of the cochleamycins, physiologically active microbial secondary metabolites, are reported. The five stereogenic centres of this subunit are introduced in high stereoselectivity in a short sequence by intermolecular Diels-Alder reaction, stereoselective methylation and hydride reduction. Cyclisation via nucleophilic addition, acidic fragmentation, regioselective Shapiro reaction and inversion of a secondary alcohol are the further key steps of these syntheses. (c) 2007 Elsevier Ltd. All rights reserved.
• Towards EPC-syntheses of the structural class of cochleamycins and macquarimicins. Part 2: EPC-synthesis of the hydrindene subunit of the macquarimicins
  作者：A. Chrobok、E. Gössinger、R. Kalb、E. Orglmeister、J. Schwaiger

  DOI：10.1016/j.tet.2007.05.094

  日期：2007.8

  The EPC-synthesis of the cis- hydrindene subunit of the macquarimicins, antibiotics with antitumour and anti-inflammatory activity, has been achieved. Desymmetrization of cis-1,4-cyclopent-2-enediol was succeeded by Diels-Alder reaction and functional group transformations to a tricyclic ketone. Regio- and stereoselective methylation via Claisen condensation and hydrogenation was followed by nucleophilic, intramolecular addition, reduction and acidic fragmentation. Further functional group transformations led to the target molecule. (c) 2007 Elsevier Ltd. All rights reserved.