(1R,3R,6S)-3-<(E)-5-(1,3-dioxolan-2-yl)-3-methyl-2-pentenyl>-1,6-dimethyl-2-methylenecyclohexanebutyronitrile | 150930-76-0

• 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: (1R,3R,6S)-3-<(E)-5-(1,3-dioxolan-2-yl)-3-methyl-2-pentenyl>-1,6-dimethyl-2-methylenecyclohexanebutyronitrile
• CAS: 150930-76-0
• 化学式: C₂₂H₃₅NO₂
• 分子量: 345.525
• InChiKey: IYFCFTCCSBANDK-ZBPFHCSDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.78
• 重原子数：
  25.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  42.25
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  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 、 碳酸氢钠 、 potassium carbonate 、 对甲苯磺酸 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 生成 methyl (1R,4Z,8R,9S,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：

  methyl (1R,6S)-2-<(tert-butyldimethylsiloxy)methyl>-1,6-dimethyl-2-cyclohexene-1-propionate 在 lithium aluminium tetrahydride 、 18-冠醚-6 、 三氟甲磺酸三甲基硅酯 、 mercury(II) trifluoroacetate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 xylene 、 苯 为溶剂， 反应 101.5h， 生成 (1R,3R,6S)-3-<(E)-5-(1,3-dioxolan-2-yl)-3-methyl-2-pentenyl>-1,6-dimethyl-2-methylenecyclohexanebutyronitrile
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ja00087a023