9,14-dideuterio-de-A,B-cholest-8-en-8-yl trifluoromethanesulfonate | 145671-01-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 9,14-dideuterio-de-A,B-cholest-8-en-8-yl trifluoromethanesulfonate
• 英文别名: [(1R,3aR,7aR)-3a,5-dideuterio-7a-methyl-1-[(2R)-6-methylheptan-2-yl]-2,3,6,7-tetrahydro-1H-inden-4-yl] trifluoromethanesulfonate
• CAS: 145671-01-8
• 化学式: C₁₉H₃₁F₃O₃S
• 分子量: 398.499
• InChiKey: POZFYEWDERNQSC-YPQGPUMKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  9,14-dideuterio-de-A,B-cholest-8-en-8-yl trifluoromethanesulfonate 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：

  艾地骨化醇中间体 在 氘代甲醇-d 、 sodium 、 lithium diisopropyl amide 作用下， 生成 9,14-dideuterio-de-A,B-cholest-8-en-8-yl trifluoromethanesulfonate
  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。