(+/-)-17-Hydroxy-23-(phenylmethoxy)daphnane

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 交让木灵型生物碱
• 英文名称: (+/-)-17-Hydroxy-23-(phenylmethoxy)daphnane
• 英文别名: 2-[(1S,2R,3S,7R,10S,13S,14S)-1-methyl-2-(3-phenylmethoxypropyl)-12-azapentacyclo[8.6.0.02,13.03,7.07,12]hexadecan-14-yl]propan-2-ol
• 化学式: C₂₉H₄₃NO₂
• 分子量: 437.666
• InChiKey: IIBPJCLQSGHCLR-GBQSPGHVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  32.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-17-Hydroxy-23-(phenylmethoxy)daphnane 在 吡啶 、 氯化亚砜 作用下， 反应 1.0h， 以53%的产率得到(+/-)-3,17-Didehydro-23-(phenylmethoxy)daphnane
  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：

  在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 (+/-)-17-Hydroxy-23-(phenylmethoxy)daphnane
  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

文献信息

• Daphniphyllum Alkaloids. 17. A Possibly Biomimetic Transformation of the Secodaphnane to the Daphnane Skeleton
  作者：Clayton H. Heathcock、Daisy Joe

  DOI：10.1021/jo00110a014

  日期：1995.3

  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.