(+/-)-17,18-Didehydro-23-(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane | 117959-76-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+/-)-17,18-Didehydro-23-(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane
• CAS: 117959-76-9
• 化学式: C₂₉H₄₁NO
• 分子量: 419.651
• InChiKey: LRCMJYUOJHSHQJ-LWFVSUFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.51
• 重原子数：
  31.0
• 可旋转键数：
  7.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  21.26
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (+/-)-17,18-Didehydro-23-(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane 在 palladium(II) trifluoroacetate 、 三苯基膦 、 对苯醌 作用下， 以 乙腈 为溶剂， 以74%的产率得到rac-(3aR,5aS,6S,8aR,11aR,11bR,11cS,12R)-11b-(3-(benzyloxy)propyl)-5a-methyl-3-methylenetetradecahydro-2H-1,6,8a-(epimethanetriyl)azuleno[5,4-g]indole
  参考文献：
  名称：

  Daphniphyllum alkaloids. 14. Total synthesis of (.+-.)-bukittinggine

  摘要：

  The unique heptacyclic Daphniphyllum alkaloid bukittinggine (1) has been prepared by total synthesis. The basic secodaphnane nucleus was fashioned in one step by application of the tetracyclization process to dihydroxy diether 5. The pyrrolidine ring in 1 was formed by a Pd(II)-catalyzed oxidative cyclization of 19 to give hexacyclic amine 32. Hydrogenation of 32 proceeded with little diastereoselectivity in establishing the final stereocenter in 1. However, when 32 was treated to the sequence of hydroboration/oxidation, tosylation, and reduction, excellent control of stereochemistry was observed in the formation of 33. Debenzylation of 33 (Na-liquid NH3), followed by regiospecific oxidative lactonization of diol 36 (Fetizon's reagent), afforded (+/-)-bukittinggine (1). The synthesis required 18 steps (9 --> 10 --> 11 --> 12 --> 13 --> 14 --> 15 --> 8 --> 16 --> 17 --> 18 --> 5 --> 19 --> 32 --> 35 --> 33 --> 36 --> 1) and delivered racemic bukittinggine in 3% overall yield.

  DOI：

  10.1021/jo00035a011
• 作为产物：
  描述：

  <1α(R^*S^*),2α,2(E)>-(+/-)-2-(4,8-Dimethyl-3,7-nonadienyl)-2-(hydroxymethyl)-β-<3-(phenylmethoxy)propyl>cyclopentaneethanol 生成 (+/-)-17,18-Didehydro-23-(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane
  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