ent-20-hydroxy-20-t-butyldimethylsilyloxy-12-oxogibberell-16-ene-7,19-dioic acid 7-methyl ester 19,20-lactone | 187329-77-7

• 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: ent-20-hydroxy-20-t-butyldimethylsilyloxy-12-oxogibberell-16-ene-7,19-dioic acid 7-methyl ester 19,20-lactone
• CAS: 187329-77-7
• 化学式: C₂₇H₄₀O₆Si
• 分子量: 488.697
• InChiKey: GVYUUGANUZMOMT-KLBYWFDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.03
• 重原子数：
  34.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  78.9
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  ent-20-hydroxy-20-t-butyldimethylsilyloxy-12-oxogibberell-16-ene-7,19-dioic acid 7-methyl ester 19,20-lactone 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以73%的产率得到ent-12α,20-dihydroxy-20-t-butyldimethylsilyloxygibberell-16-ene-7,19-dioic acid 7-methyl ester 19,20-lactone
  参考文献：
  名称：

  Synthesis of 12-hydroxy C20-gibberellins

  摘要：

  Gibberellic acid (GA(3)) (6) has been converted into 12-hydroxylated derivatives of gibberellins GA(19) and GA(24) with a view to confirming tentative assignments of structure to 12-hydroxy C-20-gibberellins isolated from several plant species. The conversions were initiated by reducing 12-substituted analogues of 6 with Li-NH3 to afford either diene carboxylic acid 8 or its 12 alpha-epimer, then introducing C20 substituents by means of the copper catalysed intramolecular cyclopropanations of the derived diazoketones 9 and 19. Li-NH3 reductions of the resulting cyclopropyl ketones 11 and 22 furnished ketones 12, 22 and 23, which could be oxidatively cleaved by treatment of their enolate anions with molecular oxygen, thereby providing the key intermediate aldehydes 13, 24 and 25 from which the target GAs could be prepared. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(96)01109-x
• 作为产物：
  描述：

  methyl ent-12β-methoxymethoxy-19-oxo-19,20-cyclogibberell-16-en-7-oate 在 4-二甲氨基吡啶 、 sodium hydroxide 、 二甲基溴化硼 、 氧气 、 potassium hydride 、 戴斯-马丁氧化剂 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 5.07h， 生成 ent-20-hydroxy-20-t-butyldimethylsilyloxy-12-oxogibberell-16-ene-7,19-dioic acid 7-methyl ester 19,20-lactone
  参考文献：
  名称：

  Synthesis of 12-hydroxy C20-gibberellins

  摘要：

  Gibberellic acid (GA(3)) (6) has been converted into 12-hydroxylated derivatives of gibberellins GA(19) and GA(24) with a view to confirming tentative assignments of structure to 12-hydroxy C-20-gibberellins isolated from several plant species. The conversions were initiated by reducing 12-substituted analogues of 6 with Li-NH3 to afford either diene carboxylic acid 8 or its 12 alpha-epimer, then introducing C20 substituents by means of the copper catalysed intramolecular cyclopropanations of the derived diazoketones 9 and 19. Li-NH3 reductions of the resulting cyclopropyl ketones 11 and 22 furnished ketones 12, 22 and 23, which could be oxidatively cleaved by treatment of their enolate anions with molecular oxygen, thereby providing the key intermediate aldehydes 13, 24 and 25 from which the target GAs could be prepared. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(96)01109-x