(4Z,8E)-(1R,11R,14S)-1,8,14-Trimethyl-15-methylene-bicyclo[9.3.1]pentadeca-4,8-diene-4-carbaldehyde | 150930-78-2

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: (4Z,8E)-(1R,11R,14S)-1,8,14-Trimethyl-15-methylene-bicyclo[9.3.1]pentadeca-4,8-diene-4-carbaldehyde
• CAS: 150930-78-2
• 化学式: C₂₀H₃₀O
• 分子量: 286.458
• InChiKey: MPLUNGPIOXCUQV-OYGRNLKSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.63
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (4Z,8E)-(1R,11R,14S)-1,8,14-Trimethyl-15-methylene-bicyclo[9.3.1]pentadeca-4,8-diene-4-carbaldehyde 在 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 作用下， 以 叔丁醇 为溶剂， 反应 10.0h， 以6.5 mg的产率得到(4Z,8E)-(1R,11R,14S)-1,8,14-Trimethyl-15-methylene-bicyclo[9.3.1]pentadeca-4,8-diene-4-carboxylic acid
  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
• 作为产物：
  描述：

  ((1′S,7a′R)-7a′-methyl-1′,2′,3′,6′,7′,7a′-hexahydrospiro[[1,3]dithiolane-2,5′-inden]-1′-yl)methanol 在 吡啶 、 咪唑 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 18-冠醚-6 、 三氟甲磺酸三甲基硅酯 、 氢氟酸 、 水 、 mercury(II) trifluoroacetate 、 silica gel 、 二异丁基氢化铝 、 三乙基硼氢化锂 、 potassium carbonate 、 对甲苯磺酸 、 三乙胺 、 间氯过氧苯甲酸 、 thallium(III) nitrate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 、 乙腈 、 xylene 、 苯 为溶剂， 反应 244.58h， 生成 (4Z,8E)-(1R,11R,14S)-1,8,14-Trimethyl-15-methylene-bicyclo[9.3.1]pentadeca-4,8-diene-4-carbaldehyde
  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