methyl (1R,4Z,8E,11R,14S)-1,8,14-trimethyl-15-methylenebicyclo<9.3.1>pentadeca-4,8-diene-4-carboxylate | 150930-68-0

• 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 (1R,4Z,8E,11R,14S)-1,8,14-trimethyl-15-methylenebicyclo<9.3.1>pentadeca-4,8-diene-4-carboxylate
• 英文别名: methyl (1R,4Z,8E,11R,14S)-1,8,14-trimethyl-15-methylidenebicyclo[9.3.1]pentadeca-4,8-diene-4-carboxylate
• CAS: 150930-68-0
• 化学式: C₂₁H₃₂O₂
• 分子量: 316.484
• InChiKey: ZMBYLHQFTJCSOJ-XMCXYFRBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl (1R,4Z,8E,11R,14S)-1,8,14-trimethyl-15-methylenebicyclo<9.3.1>pentadeca-4,8-diene-4-carboxylate 在 碘 、 silver(l) oxide 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成 methyl (1R,4Z,8S,11R,14S)-8,9-epoxy-1,8,14-trimethyl-15-methylenebicyclo<9.3.1>pentadec-4-ene-4-carboxylate
  参考文献：
  名称：

  Enantioselective synthesis of (+)-cleomeolide, the structurally unique diterpene lactone constituent of Cleome viscosa

  摘要：

  The first total synthesis of (+)-cleomeolide has been accomplished in enantioselective fashion from optically pure Wieland-Miescher ketone.

  DOI：

  10.1016/s0040-4039(00)73626-4
• 作为产物：
  描述：

  (1R,3R,6S)-3-<(E)-5-(1,3-dioxolan-2-yl)-3-methyl-2-pentenyl>-1,6-dimethyl-2-methylenecyclohexanebutyronitrile 在 sodium chlorite 、 2-甲基-2-丁烯 、 18-冠醚-6 、 水 、 二异丁基氢化铝 、 potassium carbonate 、 对甲苯磺酸 、 lithium diisopropyl amide 作用下， 以 乙醚 、 甲苯 为溶剂， 生成 methyl (1R,4Z,8E,11R,14S)-1,8,14-trimethyl-15-methylenebicyclo<9.3.1>pentadeca-4,8-diene-4-carboxylate
  参考文献：
  名称：

  Enantioselective synthesis of (+)-cleomeolide, the structurally unique diterpene lactone constituent of Cleome viscosa

  摘要：

  The first total synthesis of (+)-cleomeolide has been accomplished in enantioselective fashion from optically pure Wieland-Miescher ketone.

  DOI：

  10.1016/s0040-4039(00)73626-4

文献信息

• Enantioselective synthesis of (+)-cleomeolide, the structurally unique diterpene lactone constituent of Cleome viscosa
  作者：Leo A. Paquette、Wang Ting-Zhong、Shaopeng Wang、Christophe M.G. Philippo

  DOI：10.1016/s0040-4039(00)73626-4

  日期：1993.5

  The first total synthesis of (+)-cleomeolide has been accomplished in enantioselective fashion from optically pure Wieland-Miescher ketone.
• Total Synthesis of the Cembranoid Diterpene Lactone (+)-Cleomeolide. Some Remarkable Conformational Features of Nine-Membered Belts Linked in 2,6-Fashion to a Methylenecyclohexane Core
  作者：Leo A. Paquette、Ting-Zhong Wang、Christophe M. G. Philippo、Shaopeng Wang

  DOI：10.1021/ja00087a023

  日期：1994.4

  The total synthesis of (+)-cleomeolide (1) has been accomplished. The key construction elements of this cembranoid lactone were (i) improved conversion of optically pure Wieland-Miescher ketone into dienol ether 12 and oxidative cleavage of the latter to aldehydo ester 13; (ii) avoidance of complications arising from steric blockade of C-15 for introduction of the methylene group at that site; (iii) exploitation of an intramolecular Wadsworth-Emmons cyclization for macrocyclic ring construction; (iv) modulation of the conformation adopted by the medium ring by diastereofacial control of epoxidation of the C-3/C-4 double bond; and (v) intramolecular cyclization of the epoxy acid derived from 27 by nucleophilic capture at the more substituted oxiranyl carbon to deliver the target molecule. The deep-seated topographical change that accompanies the formation of 29 projects the macrocyclic ring quasi-axially from the methylenecyclohexane subunit in the manner known by X-ray crystallography to be adopted by the target compound. The intramolecular cyclization to set the bridgehead double bond was thereby facilitated.