(3α,3aβ,6α,6aα,9aR^*,10S^*)-(+/-)-2,3,3a,6,6a,7,8,9-Octahydro-10-methyl-10-(4-methyl-3-pentenyl)-6-<3-(phenylmethoxy)propyl>-3,6-methano-1H-dicyclopentapyridine | 117959-78-1

• 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: (3α,3aβ,6α,6aα,9aR^*,10S^*)-(+/-)-2,3,3a,6,6a,7,8,9-Octahydro-10-methyl-10-(4-methyl-3-pentenyl)-6-<3-(phenylmethoxy)propyl>-3,6-methano-1H-dicyclopentapyridine
• 英文别名: (1R,2R,6R,9S,10R,13S)-13-methyl-13-(4-methylpent-3-enyl)-1-(3-phenylmethoxypropyl)-11-azatetracyclo[7.3.1.02,6.06,10]tridec-11-ene
• CAS: 117959-78-1
• 化学式: C₂₉H₄₁NO
• 分子量: 419.651
• InChiKey: YKTXULJQGLYJGH-MWJQJBPESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3α,3aβ,6α,6aα,9aR^*,10S^*)-(+/-)-2,3,3a,6,6a,7,8,9-Octahydro-10-methyl-10-(4-methyl-3-pentenyl)-6-<3-(phenylmethoxy)propyl>-3,6-methano-1H-dicyclopentapyridine 在 盐酸 、 sodium cyanoborohydride 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以75%的产率得到(3α,3aβ,6α,6aα,9aR*,10S*)-(+/-)-Decahydro-10-methyl-10-(4-methyl-3-pentenyl)-6-<3-(phenylmethoxy)propyl>-3,6-methano-1H-dicyclopentapyridine
  参考文献：
  名称：

  Daphniphyllum Alkaloids. 17. A Possibly Biomimetic Transformation of the Secodaphnane to the Daphnane Skeleton

  摘要：

  An investigation of conversion of the secodaphnane to the daphnane skeleton has been carried out. Treatment of oxaziridine 16 with various Lewis acids resulted in rearrangements involving migration of the C15-C16 bond. However, oxazolidine 28, in which the N-O bond is constrained to be roughly antiperiplanar to the C12-C16 bond, ionizes with predominant cleavage of this C-C bond when treated with a variety of trialkylaluminum reagents. The preferred reagent for simple cleavage of the C12-C16 bond is trimethylaluminum, which converts 28 into unsaturated imines 30-32 in approximately 90% yield. The major isomer of this fragmentation process, compound 30, was converted by the process summarized in Scheme 10 into (+/-)-daphnan-23-ol (43), which has previously been converted into (+/-)-methyl homodaphniphyllate (44). Remarkably, conditions were also found that convert 28 directly into the daphnane skeleton. For example, 28 reacts with diisobutylaluminum hydride in toluene to give daphnanes 34 and 35 in approximately 80% yield.

  DOI：

  10.1021/jo00110a014
• 作为产物：
  描述：

  5-苄氧基戊酸 在 盐酸 、 氢氧化钾 、 lithium aluminium tetrahydride 、 ammonium acetate 、 氨 、 二异丁基氢化铝 、 溶剂黄146 、 N,N'-羰基二咪唑 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 9.08h， 生成 (3α,3aβ,6α,6aα,9aR^*,10S^*)-(+/-)-2,3,3a,6,6a,7,8,9-Octahydro-10-methyl-10-(4-methyl-3-pentenyl)-6-<3-(phenylmethoxy)propyl>-3,6-methano-1H-dicyclopentapyridine
  参考文献：
  名称：

  Daphniphyllum alkaloids. 11. Biomimetic total synthesis of methyl homosecodaphniphyllate. Development of the tetracyclization reaction

  摘要：

  A biomimetic total synthesis of (+/-)-methyl homosecodaphniphyllate has been developed. The synthesis starts with a triply convergent, tandem Michael addition-enolate alkylation, wherein amide 9, enoate 7, and alkyl iodide 5 are assembled in essentially quantitative yield to obtain compounds 13, 14, and 15. The major isomer 13 is converted in three steps into a 1:1 mixture of diols 18a and 18b. These diols are subjected to a two-step process involving Swern oxidation and treatment of the resulting dialdehyde sequentially with ammonia and acetic acid; pentacyclic unsaturated amine 23 is obtained in 82% yield. Three additional functional group steps are used to convert 23 into racemic methyl homosecodaphniphyllate ((+/-)-4). The synthesis requires nine steps and proceeds in 48% overall yield from 5, 7, and 9. The tetracyclization process was shown to proceed via dialdehyde 26, tricyclic aza diene 27, and tetracyclic imine 28. An interesting and potentially useful variant of the tetracyclization procedure employs methylamine or benzylamine instead of ammonia. In this modification, the final reaction product is pentacyclic amine 29, in which the isopropenyl double bond has also been reduced. It is suggested that this reduction occurs by intramolecular hydride transfer at the stage of cationic intermediate 33.

  DOI：

  10.1021/jo00035a008