(1R,3S,5Z)-5-[(2E)-2-[(1R,3aS,7aR)-1-[(E,2R,5S)-5-cyclopropyl-6-(methoxymethoxy)-6-methylhept-3-en-2-yl]-7a-methyl-2,3,3a,5,6,7-hexahydro-1H-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol | 1026686-28-1

• 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: (1R,3S,5Z)-5-[(2E)-2-[(1R,3aS,7aR)-1-[(E,2R,5S)-5-cyclopropyl-6-(methoxymethoxy)-6-methylhept-3-en-2-yl]-7a-methyl-2,3,3a,5,6,7-hexahydro-1H-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol
• CAS: 1026686-28-1
• 化学式: C₃₂H₅₀O₄
• 分子量: 498.747
• InChiKey: YWQOEZKEJUXIIV-BYHDZLHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,3S,5Z)-5-[(2E)-2-[(1R,3aS,7aR)-1-[(E,2R,5S)-5-cyclopropyl-6-(methoxymethoxy)-6-methylhept-3-en-2-yl]-7a-methyl-2,3,3a,5,6,7-hexahydro-1H-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol 在 AG₅₀ WX₄ resin 作用下， 以 甲醇 为溶剂， 生成 (1R,3S,5Z)-5-[(2E)-2-[(1R,3aS,7aR)-1-[(E,2R,5S)-5-cyclopropyl-6-hydroxy-6-methylhept-3-en-2-yl]-7a-methyl-2,3,3a,5,6,7-hexahydro-1H-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol
  参考文献：
  名称：

  A Short, Efficient Copper-Mediated Synthesis of 1α,25-Dihydroxyvitamin D₂ (1α,25-Dihydroxyergocalciferol) and C-24 Analogs^1,2

  摘要：

  Two synthetic routes to the nonnatural hormone 1 alpha,25-dihydroxyergocalciferol [2b, 1 alpha,25-(OH)(2)-D-2] and analogs modified at C-24 have been developed both starting from aldehyde 7b. Key steps in route A (eight steps, approximate to 38% overall yield from 7b) are (1) stereoselective addition of (E)-vinyllithium reagent 8c to aldehyde 7b; and (2) S(N)2' anti-displacement of the allylic phosphate of 5e by organocuprates derived from Grignard reagents and CuCN in the presence of LiCl. Key steps in route B (eight steps from 7b, 48% overall yield) are (1) Wittig-Horner type coupling between ketone 22, which bears an allylic phosphate group on the side chain, and the ylide derived from the Lythgoe-Roche phosphine oxide to form the vitamin D triene unit; and (2) efficient S(N)2' anti-displacement of the phosphate group of 23 by the organocuprate derived from MeMgCl, CuCN, and LiCl, without affecting the labile vitamin D triene system, to give, after deprotection, 1 alpha,25-(OH)2-D-2. Route B is particularly attractive as an approach to diverse C-24 vitamin D analogs for biological screening.

  DOI：

  10.1021/jo970604u
• 作为产物：
  描述：

  [(1R,3aR,4S,7aR)-1-[(E,2R,5S)-5-cyclopropyl-6-(methoxymethoxy)-6-methylhept-3-en-2-yl]-7a-methyl-1,2,3,3a,4,5,6,7-octahydroinden-4-yl]oxy-tert-butyl-dimethylsilane 在 重铬酸吡啶 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 苯基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 28.67h， 生成 (1R,3S,5Z)-5-[(2E)-2-[(1R,3aS,7aR)-1-[(E,2R,5S)-5-cyclopropyl-6-(methoxymethoxy)-6-methylhept-3-en-2-yl]-7a-methyl-2,3,3a,5,6,7-hexahydro-1H-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol
  参考文献：
  名称：

  A Short, Efficient Copper-Mediated Synthesis of 1α,25-Dihydroxyvitamin D₂ (1α,25-Dihydroxyergocalciferol) and C-24 Analogs^1,2

  摘要：

  Two synthetic routes to the nonnatural hormone 1 alpha,25-dihydroxyergocalciferol [2b, 1 alpha,25-(OH)(2)-D-2] and analogs modified at C-24 have been developed both starting from aldehyde 7b. Key steps in route A (eight steps, approximate to 38% overall yield from 7b) are (1) stereoselective addition of (E)-vinyllithium reagent 8c to aldehyde 7b; and (2) S(N)2' anti-displacement of the allylic phosphate of 5e by organocuprates derived from Grignard reagents and CuCN in the presence of LiCl. Key steps in route B (eight steps from 7b, 48% overall yield) are (1) Wittig-Horner type coupling between ketone 22, which bears an allylic phosphate group on the side chain, and the ylide derived from the Lythgoe-Roche phosphine oxide to form the vitamin D triene unit; and (2) efficient S(N)2' anti-displacement of the phosphate group of 23 by the organocuprate derived from MeMgCl, CuCN, and LiCl, without affecting the labile vitamin D triene system, to give, after deprotection, 1 alpha,25-(OH)2-D-2. Route B is particularly attractive as an approach to diverse C-24 vitamin D analogs for biological screening.

  DOI：

  10.1021/jo970604u