(4,4-Dimethoxycyclohexen-1-yl)methanol | 72445-27-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4,4-Dimethoxycyclohexen-1-yl)methanol
• CAS: 72445-27-3
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: VOMFTMKSYUYGDY-UHFFFAOYSA-N

物化性质

• 沸点：
  244.2±40.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  (4,4-Dimethoxycyclohexen-1-yl)methanol 在 4-二甲氨基吡啶 、 potassium osmate(VI) 、 Hydroquinone 1,4-phthalazinediyl diether 、 甲基磺酰胺 、 potassium carbonate 、 三乙胺 、 potassium hexacyanoferrate(III) 作用下， 以 二氯甲烷 、 叔丁醇 为溶剂， 反应 9.0h， 生成 (1S,2S)-1-(((4-methoxybenzoyl)oxy)methyl)-4,4-dimethoxy-1,2-cyclohexanediol
  参考文献：
  名称：

  The application of a mechanistic model leads to the extension of the Sharpless asymmetric dihydroxylation to allylic 4-methoxybenzoates and conformationally related amine and homoallylic alcohol derivatives.

  摘要：

  The scope and utility of the Sharpless asymmetric dihydroxylation has been expanded to include the use of allylic 4-methoxybenzoates as precursors of a wide variety of substituted chiral glycerol derivatives. The allylic 4-methoxybenzoyl group was found to be superior to other allylic alcohol protecting groups with respect to both yield and enantiomeric purity of the product. For example, asymmetric dihydroxylation of allyl 4-methoxybenzoate (6a) using the (DHQD)(2)PYDZ . OsO4 (1 . OsO4) catalyst system affords (S)-3-(4-methoxybenzoyloxy)-1,2-propanediol (7a) in >99% yield and 98% ee. The 4-methoxybenzoates of a variety of other allylic alcohols also serve as excellent substrates, in contrast to the parent alcohols themselves. The efficient asymmetric dihydroxylation of homoallylic 4-methoxyphenyl ethers (12a and 15), allyl 9-fluorenimine (18b), bis(homoallyl) 4-methoxybenzoate (14) and other structurally related substrates is also described. This methodology was developed under mechanistic guidance from the transition state model advanced earlier by us for the bis-cinchona alkaloid catalyzed asymmetric dihydroxylation reaction. The 4-methoxybenzoyl group functions not only to selectively protect one of the hydroxy groups of the product triol for subsequent synthetic manipulation but also to provide an extended binding group that participates in hydrophobic and aryl-aryl interactions with the U-shaped binding pocket of the (DHQD)(2)PYDZ . OsO4 catalyst (1 . OsO4), thereby enhancing enantioselectivity.

  DOI：

  10.1021/ja00149a003
• 作为产物：
  描述：

  4-甲氧基苄醇 、 原甲酸三甲酯 在 氨 、 sodium 、 对甲苯磺酸 作用下， 生成 (4,4-Dimethoxycyclohexen-1-yl)methanol
  参考文献：
  名称：

  Short Enantioselective Synthesis of (-)-Ovalicin, a Potent Inhibitor of Angiogenesis, Using Substrate-Enhanced Catalytic Asymmetric Dihydroxylation

  摘要：

  DOI：

  10.1021/ja00105a084

文献信息

• Total synthesis of vernolepin—I
  作者：Hideo Iio、Minoru Isobe、Tatsuhiko Kawai、Toshio Goto

  DOI：10.1016/s0040-4020(01)93706-8

  日期：1979.1

  The key intermediate (9) for the total synthesis of antitumor sesquiterpene vernolepin (1) was prepared in seventeen steps from 2,5-dihydroanisyl alcohol. Intramolecular Michael addition (7→ 8) afforded the cis-2-oxadecalone system, which was stereospecifically converted to 9 by using the enolization character of 8.

  由17，2，5-二氢茴香醇制备全合成抗肿瘤倍半萜vernolepin（1）的关键中间体（9）。分子内迈克尔加成（7→8）提供了顺-2-氧杂十二酮系统，其通过使用8的烯醇化特性立体定向地转化为9。
• The application of a mechanistic model leads to the extension of the Sharpless asymmetric dihydroxylation to allylic 4-methoxybenzoates and conformationally related amine and homoallylic alcohol derivatives.
  作者：E. J. Corey、Angel Guzman-Perez、Mark C. Noe

  DOI：10.1021/ja00149a003

  日期：1995.11

  The scope and utility of the Sharpless asymmetric dihydroxylation has been expanded to include the use of allylic 4-methoxybenzoates as precursors of a wide variety of substituted chiral glycerol derivatives. The allylic 4-methoxybenzoyl group was found to be superior to other allylic alcohol protecting groups with respect to both yield and enantiomeric purity of the product. For example, asymmetric dihydroxylation of allyl 4-methoxybenzoate (6a) using the (DHQD)(2)PYDZ . OsO4 (1 . OsO4) catalyst system affords (S)-3-(4-methoxybenzoyloxy)-1,2-propanediol (7a) in >99% yield and 98% ee. The 4-methoxybenzoates of a variety of other allylic alcohols also serve as excellent substrates, in contrast to the parent alcohols themselves. The efficient asymmetric dihydroxylation of homoallylic 4-methoxyphenyl ethers (12a and 15), allyl 9-fluorenimine (18b), bis(homoallyl) 4-methoxybenzoate (14) and other structurally related substrates is also described. This methodology was developed under mechanistic guidance from the transition state model advanced earlier by us for the bis-cinchona alkaloid catalyzed asymmetric dihydroxylation reaction. The 4-methoxybenzoyl group functions not only to selectively protect one of the hydroxy groups of the product triol for subsequent synthetic manipulation but also to provide an extended binding group that participates in hydrophobic and aryl-aryl interactions with the U-shaped binding pocket of the (DHQD)(2)PYDZ . OsO4 catalyst (1 . OsO4), thereby enhancing enantioselectivity.
• Short Enantioselective Synthesis of (-)-Ovalicin, a Potent Inhibitor of Angiogenesis, Using Substrate-Enhanced Catalytic Asymmetric Dihydroxylation
  作者：E. J. Corey、Angel Guzman-Perez、Mark C. Noe

  DOI：10.1021/ja00105a084

  日期：1994.12