1α,25-dihydroxy-9,14,19,19,19-pentadeuterioprevitamin D3 | 134485-14-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 1α,25-dihydroxy-9,14,19,19,19-pentadeuterioprevitamin D3
• 英文别名: (6Z)-(1S,3R)-9,14,19,19,19-pentadeuterio-9,10-seco-5(10),6,8-cholestatriene-1,3,25-triol；(1R,3S)-5-[(Z)-2-[(1R,3aR,7aR)-3a,5-dideuterio-1-[(2R)-6-hydroxy-6-methylheptan-2-yl]-7a-methyl-2,3,6,7-tetrahydro-1H-inden-4-yl]ethenyl]-4-(trideuteriomethyl)cyclohex-4-ene-1,3-diol
• CAS: 134485-14-6
• 化学式: C₂₇H₄₄O₃
• 分子量: 421.605
• InChiKey: DOIZGAFWGREMOD-SGWDTOPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1α,25-dihydroxy-9,14,19,19,19-pentadeuterioprevitamin D3 以 丙酮 为溶剂， 反应 12.0h， 以16 mg的产率得到1α,25-dihydroxy-9,14,19,19,19-pentadeuteriovitamin D3
  参考文献：
  名称：

  Vitamin D (calciferol) and its analogs. 40. 1.alpha.,25-Dihydroxyprevitamin D3: synthesis of the 9,14,19,19,19-pentadeuterio derivative and a kinetic study of its [1,7]-sigmatropic shift to 1.alpha.,25-dihydroxyvitamin D3

  摘要：

  The hormonally active steroid 1-alpha, 25-dihydroxyvitamin D3 (3) exists in equilibrium with its previtamin form 5. In an attempt to further understand the significance of this previtamin and previtamin D's in general, the pentadeuterio analogue of 5 was synthesized. Accordingly, 9, 14, 19, 19, 19-pentadeuterio-1-alpha, 25-dihydroxyprevitamin D3 (6) was prepared from the readily available, optically active synthons (S)-(+)-carvone (10) and the Inhoffen-Lythgoe diol (9). A general method was developed to regioselectively deuteriate beta-methyl-alpha,beta-unsaturated aldehydes via their Schiff bases and was used in the synthesis to convert aldehyde 16a to its deuteriated analogue 16b. Thermolysis of 6 afforded 9, 9, 14, 19, 19-pentadeuterio-1-alpha,25-dihydroxyvitamin D3 (24). A kinetic investigation of the [1, 7]-sigmatropic hydrogen (deuterium) shifts which convert previtams 5 and 6 to vitamins 3 and 24, respectively, revealed that at 25-degrees-C the process proceeds with a relatively normal primary kinetic isotope effect, k(H)/k(D), of 5.5.

  DOI：

  10.1021/ja00018a038
• 作为产物：
  描述：

  de-A,B-25-cholesten-8-one 在 Lindlar's catalyst 喹啉 、 sodium hydroxide 、 sodium tetrahydroborate 、 copper(l) iodide 、 氘代甲醇-d 、 bispalladium(II) acetate 、 mercury(II) diacetate 、 四丁基氟化铵 、 氢气 、 sodium methylate 、 二乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 102.41h， 生成 1α,25-dihydroxy-9,14,19,19,19-pentadeuterioprevitamin D3
  参考文献：
  名称：

  Vitamin D (calciferol) and its analogs. 40. 1.alpha.,25-Dihydroxyprevitamin D3: synthesis of the 9,14,19,19,19-pentadeuterio derivative and a kinetic study of its [1,7]-sigmatropic shift to 1.alpha.,25-dihydroxyvitamin D3

  摘要：

  The hormonally active steroid 1-alpha, 25-dihydroxyvitamin D3 (3) exists in equilibrium with its previtamin form 5. In an attempt to further understand the significance of this previtamin and previtamin D's in general, the pentadeuterio analogue of 5 was synthesized. Accordingly, 9, 14, 19, 19, 19-pentadeuterio-1-alpha, 25-dihydroxyprevitamin D3 (6) was prepared from the readily available, optically active synthons (S)-(+)-carvone (10) and the Inhoffen-Lythgoe diol (9). A general method was developed to regioselectively deuteriate beta-methyl-alpha,beta-unsaturated aldehydes via their Schiff bases and was used in the synthesis to convert aldehyde 16a to its deuteriated analogue 16b. Thermolysis of 6 afforded 9, 9, 14, 19, 19-pentadeuterio-1-alpha,25-dihydroxyvitamin D3 (24). A kinetic investigation of the [1, 7]-sigmatropic hydrogen (deuterium) shifts which convert previtams 5 and 6 to vitamins 3 and 24, respectively, revealed that at 25-degrees-C the process proceeds with a relatively normal primary kinetic isotope effect, k(H)/k(D), of 5.5.

  DOI：

  10.1021/ja00018a038