methyl (3aR,5aR,8aR,9aS)-8-hydroxy-3a-methyl-2,3,3a,4,5,8,9,9a-octahydro-5aH-cyclopenta[a]naphthalene-5a-carboxylate | 467242-44-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (3aR,5aR,8aR,9aS)-8-hydroxy-3a-methyl-2,3,3a,4,5,8,9,9a-octahydro-5aH-cyclopenta[a]naphthalene-5a-carboxylate
• 英文别名: methyl (3aR,5aR,8R,9aS)-8-hydroxy-3a-methyl-3,4,5,8,9,9a-hexahydro-2H-cyclopenta[a]naphthalene-5a-carboxylate
• CAS: 467242-44-0
• 化学式: C₁₆H₂₂O₃
• 分子量: 262.349
• InChiKey: QDGYSGRSTHASSI-YUDUHTQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (3aR,5aR,8aR,9aS)-8-hydroxy-3a-methyl-2,3,3a,4,5,8,9,9a-octahydro-5aH-cyclopenta[a]naphthalene-5a-carboxylate 在 manganese(IV) oxide 、 sodium hydroxide 、 sodium tetrahydroborate 、 4 A molecular sieve 、 二苯基二硒醚 、 双氧水 、 sodium acetate 、 lithium 、 溶剂黄146 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氨 、 甲苯 、 叔丁醇 为溶剂， 反应 18.0h， 生成 (3aR,5aR,9aS)-3a-Methyl-8-oxo-2,3,3a,4,5,6,7,8,9,9a-decahydro-cyclopenta[a]naphthalene-5a-carboxylic acid methyl ester
  参考文献：
  名称：

  Synthetic studies toward cyathin diterpenoids: approach to the tricyclic system through intramolecular Heck-type cyclization

  摘要：

  The enantioselective synthesis of a model of the core ring system of cyathin diterpenes is described. The key tricyclic acetate 4 was assembled via an intramolecular Heck-type cyclization of the chiral triflate 8. Acetate 4 was taken through to model cyathan ketones 3a and 3b by a one-carbon ring expansion. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00570-1
• 作为产物：
  描述：

  methyl (3aR,5aR,8R,9aS)-8-acetyloxy-3a-methyl-3,4,5,8,9,9a-hexahydro-2H-cyclopenta[a]naphthalene-5a-carboxylate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以96%的产率得到methyl (3aR,5aR,8aR,9aS)-8-hydroxy-3a-methyl-2,3,3a,4,5,8,9,9a-octahydro-5aH-cyclopenta[a]naphthalene-5a-carboxylate
  参考文献：
  名称：

  Synthetic studies toward cyathin diterpenoids: approach to the tricyclic system through intramolecular Heck-type cyclization

  摘要：

  The enantioselective synthesis of a model of the core ring system of cyathin diterpenes is described. The key tricyclic acetate 4 was assembled via an intramolecular Heck-type cyclization of the chiral triflate 8. Acetate 4 was taken through to model cyathan ketones 3a and 3b by a one-carbon ring expansion. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00570-1

文献信息

• Synthetic Studies on Cyathin Terpenoids: Enantioselective Synthesis of the Tricyclic Core of Cyathin through Intramolecular Heck Cyclisation
  作者：Emmanuelle Drège、Cyrille Tominiaux、Georges Morgant、Didier Desmaële

  DOI：10.1002/ejoc.200600429

  日期：2006.11

  An enantioselective synthesis of the tricyclic ketone (+)-5, which displays the carbon core of NGF-inducing cyathane diterpenes, has been completed according to a strategy in which the key step was the intramolecular Heck reaction of the AC subunit 49 establishing the crucial anti stereochemical relationship between the two angular substituents. The C-9 quaternary centre was set up by taking advantage

  三环酮 (+)-5 的对映选择性合成，显示了 NGF 诱导的氰基二萜的碳核心，已根据一种策略完成，其中关键步骤是 AC 亚基 49 的分子内 Heck 反应建立关键的两个角取代基之间的反立体化学关系。C-9 四元中心是通过利用涉及手性亚胺的对映选择性迈克尔加成建立的，提供 91% ee 的酮酯 (R)-10。在丙酸酯侧链引入异丙基和碘脱羧基后，碘酮 39 与二氢苯甲酸甲酯的烯醇锂缩合得到 AC 亚基 43，该亚基进一步细化为三氟甲磺酸酯 (-)-22。虽然 22 的直接 Heck 环化是无效的，1,4-环己二烯部分的双（烯丙基）位置的氧化增强了反应性，允许立体选择性地形成六氢-环戊二烯（+）-50a。该结构的一个关键要素是最终的 C 环扩大，涉及三甲基铝促进酮 52 与三甲基甲硅烷基重氮甲烷的单碳膨胀，提供三环酮 (+)-5。此外，三烯酮 (+)-50a 的环氧化反应仅发生在 β 面上，产生
• Synthetic studies toward cyathin diterpenoids: approach to the tricyclic system through intramolecular Heck-type cyclization
  作者：Cyrille Thominiaux、Angèle Chiaroni、Didier Desmaële

  DOI：10.1016/s0040-4039(02)00570-1

  日期：2002.5

  The enantioselective synthesis of a model of the core ring system of cyathin diterpenes is described. The key tricyclic acetate 4 was assembled via an intramolecular Heck-type cyclization of the chiral triflate 8. Acetate 4 was taken through to model cyathan ketones 3a and 3b by a one-carbon ring expansion. (C) 2002 Elsevier Science Ltd. All rights reserved.