(1S)-(-)-3-ethynyl-4-(trideuteriomethyl)cyclohex-3-en-1-ol | 145640-27-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S)-(-)-3-ethynyl-4-(trideuteriomethyl)cyclohex-3-en-1-ol
• 英文别名: (1S)-3-ethynyl-4-(trideuteriomethyl)cyclohex-3-en-1-ol
• CAS: 145640-27-3
• 化学式: C₉H₁₂O
• 分子量: 139.17
• InChiKey: PLLPCYXAEHFXRV-IZTXOYSKSA-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：

  (1S)-(-)-3-ethynyl-4-(trideuteriomethyl)cyclohex-3-en-1-ol 在 Lindlar's catalyst 、 bispalladium(II) acetate 喹啉 、 copper(l) iodide 、 氢气 、 二乙胺 作用下， 以 正己烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 previtamin D₃-d5
  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
• 作为产物：
  描述：

  4-[[(1,1-二甲基乙基)二苯基甲硅烷基]氧基]-环己酮 在 正丁基锂 、 四丁基氟化铵 、 sodium hydride 、 magnesium sulfate 、 对甲苯磺酸 、 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 、 paraffin 、 苯 为溶剂， 反应 16.5h， 生成 (1S)-(-)-3-ethynyl-4-(trideuteriomethyl)cyclohex-3-en-1-ol
  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