(S)-1-Ethynyl-5-hydroxy-2-methyl-1-cyclohexene | 29569-75-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-1-Ethynyl-5-hydroxy-2-methyl-1-cyclohexene
• 英文别名: (1S)-(-)-3-ethynyl-4-methylcyclohex-3-en-1-ol；(S)-3-Ethinyl-4-methyl-cyclohex-3-en-1-ol；(1S)-3-ethynyl-4-methylcyclohex-3-en-1-ol
• CAS: 29569-75-3
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: PLLPCYXAEHFXRV-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-1-Ethynyl-5-hydroxy-2-methyl-1-cyclohexene 在 Pd-Pb-CaCO₃ (Lindlar catalyst) chromium(II) perchlorate 、 氢气 、 乙二胺 作用下， 以 喹啉 、 N,N-二甲基甲酰胺 、 Petroleum ether 为溶剂， 生成 3Β,6Z-9,10-断胆甾基-5(10),6,8-三烯甘油酯-3
  参考文献：
  名称：

  Calciferol及其亲戚。第十六部分。钙化甾醇3 2的全合成

  摘要：

  钙化固醇3的总合成无需使用光化学方法即可完成。9α-Chloro- des- AB -cholestan-8-one {5α-chloro-1β-[（1 R）-1,5-methyldimethylhexyl]-7aβ-methyl- trans - perhydroindan -4-one}（1; X =将（α-Cl）和（1 S）-3-乙炔基-4-甲基环己-3-烯-1-醇（2; R = H）合并得到氯醇（3; X =α-Cl），首先转化为二烯炔（4），然后通过乙炔键的半氢化反应转化为前钙化甾醇3（5）。描述了与维生素原和相关途径有关的模型实验。

  DOI：

  10.1039/j39710002960
• 作为产物：
  描述：

  1-((tert-butyldiphenylsilyl)oxy)-4-methyl-3-((n-butylthio)methylidene)cyclohex-4-ene 在 正丁基锂 、 四丁基氟化铵 、 三苯基膦 、 mercury dichloride 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 11.17h， 生成 (S)-1-Ethynyl-5-hydroxy-2-methyl-1-cyclohexene
  参考文献：
  名称：

  Studies of vitamin D (calciferol) and its analogs. 44. Thermal [1,7]-sigmatropic shift of previtamin D3 to vitamin D3: synthesis and study of pentadeuterio derivatives

  摘要：

  Specifically pentadeuteriated previtamin D3 11 has been synthesized to impart thermal stability to the otherwise labile material. A 12-step synthesis of the trideuteriated A-ring 14b from p-methoxyphenol was developed and employed the addition of (methyl-d3)magnesium iodide to either the keto thiomethylene intermediate 23 or the keto dioxane 27. The enantiomerically pure trideuterio A-ring (-)-14b was then coupled with the deuteriated CD fragment 13b followed by hydrogenation to afford pentadeuteriated previtamin D3 11. A primary deuterium kinetic isotope effect (KIE) study of the [1,7]-sigmatropic hydrogen migration in the conversion of previtamin D3 to vitamin D3 indicated a more ''normal'' primary deuterium isotope effect (as compared to a previously reported literature value of approximately 45). At 80-degrees-C, a k(H)/k(D) for the previtamin D3 to vitamin D3 isomerization was determined to be approximately 6.2. At 25-degrees-C, this [1,7]-sigmatropic hydrogen migration proceeds with a k(H)/k(D) Of approximately 11.4. The reversible, first-order [1,7]-sigmatropic hydrogen shift of previtamin D3 to D3, determined over the temperature range 60.1-85.5-degrees-C is characterized by the following activation parameters: log A(H) = 8.8 and E(a)H = 19.6 kcal/mol. Deuteriated pre-D3, which rearranges over this temperature range, is characterized by the activation parameters log A(D) = 9.5 and E(a)D = 21.9 kcal/mol.

  DOI：

  10.1021/jo00055a011

文献信息

• Tunneling in tocopherol-mediated peroxidation of 7-dehydrocholesterol
  作者：H. Muchalski、L. Xu、N. A. Porter

  DOI：10.1039/c4ob02377c

  日期：——

  We report here that H-atom tunneling facilitates the propagation step in the tocopherol-mediated peroxidation (TMP) of 7-dehydrocholesterol. This process likely becomes a major propagation pathway when radical intermediates are isolated in cellular organelles or lipid particles such as low-density lipoproteins. In TMP of 7-DHC and deuterium-reinforced 7-DHC, the KIE of removing hydrogen/deuterium at C9 was found to be 21 ± 1.

  我们在这里报告，氢原子隧道效应促进了生育酚介导的7-去氢胆固醇过氧化反应（TMP）中的传播步骤。当自由基中间体被隔离在细胞器或脂质粒子（如低密度脂蛋白）中时，这个过程可能成为主要的传播途径。在7-DHC和重氘增强的7-DHC的TMP中，发现在C9处去除氢/重氘的KIE为21±1。
• Selective Acylation of A-Ring Precursors of Vitamin D Using Enzymes in Organic Solvents
  作者：Susana Fernandez、b Miguel Ferrero、Vicente Gotor、William H. Okamura

  DOI：10.1021/jo00124a014

  日期：1995.9

  Whereas Chromobacterium viscosum lipase (CVL) catalyzes selectively the acylation of the C-5 hydroxyl of the three stereoisomeric vitamin D A-ring precursors 2a, 3a and 3b, only the C-3 hydroxyl of the fourth stereoisomer 2b is acylated under the same conditions in organic solvent. In a convenient application, the racemic vitamin D A-ring precursor 4, possessing only the C-5 hydroxyl, was resolved using suitable conditions identified from the studies of 2 and 3.