(1R,2S,3S,6R,7S,8S)-tricyclo-3-pivaloyloxy[6.2.1.0^2,7]undeca-4-en-6-ol | 148903-13-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1R,2S,3S,6R,7S,8S)-tricyclo-3-pivaloyloxy[6.2.1.0^2,7]undeca-4-en-6-ol
• 英文别名: (-)-(1R,4S,4aR,5R,8S,8aR)-1,4,4a,5,8,8a-hexahydro-5-pivaloyl-oxy-endo-1,4-methano-8-naphthol；[(1S,2R,3S,6R,7S,8R)-6-hydroxy-3-tricyclo[6.2.1.02,7]undeca-4,9-dienyl] 2,2-dimethylpropanoate
• CAS: 148903-13-3
• 化学式: C₁₆H₂₂O₃
• 分子量: 262.349
• InChiKey: LLYGSSQSUJPRLF-OKDXSUHISA-N

物化性质

• 沸点：
  363.6±42.0 °C(predicted)
• 密度：
  1.15±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,2S,3S,6R,7S,8S)-tricyclo-3-pivaloyloxy[6.2.1.0^2,7]undeca-4-en-6-ol 在 六甲基磷酰三胺 、 bis-triphenylphosphine-palladium(II) chloride 、 甲酸铵 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 0.33h， 生成 (1R,2S,5S*,7R,8S)-5-(trimethylsilyl)tricyclo<6.2.1.0^2,7>undec-9-en
  参考文献：
  名称：

  Enantiocontrolled synthesis of optically pure 5-trimethylsilyl- and 5-tributylstannyl-cyclohex-2-enones

  摘要：

  光学纯的5-三甲基硅基和5-三丁基锡基环己烯-2-酮已通过采用一种新型的钯介导消除反应作为关键步骤，从常见的手性前体高效制备。

  DOI：

  10.1039/c39930000788
• 作为产物：
  描述：

  norbornenoquinone 在 4-二甲氨基吡啶 、 二异丁基氢化铝 、 potassium carbonate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 336.0h， 生成 (1R,2S,3S,6R,7S,8S)-tricyclo-3-pivaloyloxy[6.2.1.0^2,7]undeca-4-en-6-ol
  参考文献：
  名称：

  Enantiocontrolled synthesis of optically pure 5-trimethylsilyl- and 5-tributylstannyl-cyclohex-2-enones

  摘要：

  光学纯的5-三甲基硅基和5-三丁基锡基环己烯-2-酮已通过采用一种新型的钯介导消除反应作为关键步骤，从常见的手性前体高效制备。

  DOI：

  10.1039/c39930000788

文献信息

• The enantiodivergent total synthesis of natural and unnatural enantiomers of theobroxide
  作者：Takashi Kamikubo、Kunio Ogasawara

  DOI：10.1016/0040-4039(95)00131-u

  日期：1995.3

  Both enantiomers of theobroxide, a potato micro-tuber inducing substance isolated from Lasiodiplodia theobromae, have been synthesized from a common chiral building block serving as a chiral equivalent of 1,4-dihydroxy-2,5-cyclohexadiene. The synthesis has verified the proposed structure and the absolute configuration.

  从一种常见的手性结构单元，即1,4-二羟基-2,5-环己二烯的手性等效物，合成了theobroxide的两种对映异构体，这是一种从马铃薯红孢杆菌中分离出来的马铃薯微块茎诱导物质。综合已经验证了所提出的结构和绝对构型。
• Concise enantiodivergent synthesis of eutypoxide B
  作者：Seiichi Takano、Minoru Moriya、Kunio Ogasawara

  DOI：10.1039/c39930000614

  日期：——

  The first enantiodivergent synthesis of eutypoxide B 1, a metabolite of the fungus Eutypa lata, has been accomplished in a stereo- and regio-controlled manner by using the single chiral building block 3 as a chiral equivalent of (Z)-cyclohex-2,5-dien-1,4-diol 2.

  通过使用单一手性结构单元3作为（Z）-cyclohex-2的手性等效物，以立体和区域控制的方式完成了首个对映体合成的优古缇氧化物B 1（真菌Eutypa lata的代谢物）的合成。5-二烯-1，4-二醇2。
• Enantiodivergent Preparation of Chiral 2,5-Cyclohexadienone Synthons
  作者：Seiichi Takano、Yasuhiro Higashi、Takashi Kamikubo、Minoru Moriya、Kunio Ogasawara

  DOI：10.1055/s-1993-25973

  日期：——

  Expedient enantiodivergent synthesis of synthons of two 2,5-cyclohexadienone derivatives has been developed using the common chiral building block obtained by lipase-mediated asymmetrization of the meso-symmetric starting material.

  利用脂肪酶介导的中不对称起始材料不对称化得到的共用手性结构单元，开发出了两种 2,5-Cyclohexadienone 衍生物的对映体异构合成方法。
• Absolute Configuration of (+)-PT-Toxin: Enantiodivergent Synthesis of (+)- and (-)-PT-Toxins
  作者：Kunio Ogasawara、Takashi Kamikubo

  DOI：10.3987/com-97-s(n)5

  日期：——
• Asymmetric Acylation of <i>s</i><i>ec</i>-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1021/jo990892p

  日期：1999.12.1

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.