(+/-)-allo-7,8-dimethoxy-13,14-didehydro-18-oxoberban | 132628-53-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: (+/-)-allo-7,8-dimethoxy-13,14-didehydro-18-oxoberban
• 英文别名: (8aS,12aR,13aS)-2,3-dimethoxy-5,6,8a,9,10,12a,13,13a-octahydroisoquinolino[2,1-b]isoquinolin-8-one
• CAS: 132628-53-6
• 化学式: C₁₉H₂₃NO₃
• 分子量: 313.397
• InChiKey: JAEXTPALVDKMCH-NOLJZWGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-allo-7,8-dimethoxy-13,14-didehydro-18-oxoberban 在 platinum(IV) oxide lithium aluminium tetrahydride 、 氢气 作用下， 生成 allo-7,8-dimethoxyberbane
  参考文献：
  名称：

  Bicycloannulation of C=N Double Bonds through Organotin-Aided Three Component Coupling. A Short and Stereoselective Synthesis of (±)-allo-Berbane and (±)-allo-Yohimbane Systems

  摘要：

  有机锡辅助的 C=N 双键与 2,4-戊二烯基和 α,β-不饱和酰基的三组分偶联，然后发生分子内 Diels-Alder 反应，导致 C=N 双键高度立体选择性双环化，从而在一烧瓶操作中得到烯丙基苄基和烯丙基育亨烷体系。

  DOI：

  10.1246/cl.1990.2161
• 作为产物：
  描述：

  6,7-二甲氧基-3,4-二氢异喹啉 、 tributyl(2,4-pentadienyl)stannane 、 丙烯酰氯 以 二氯甲烷 为溶剂， 以81%的产率得到(+/-)-allo-7,8-dimethoxy-13,14-didehydro-18-oxoberban
  参考文献：
  名称：

  Bicycloannulation of C=N Double Bonds through Organotin-Aided Three Component Coupling. A Short and Stereoselective Synthesis of (±)-allo-Berbane and (±)-allo-Yohimbane Systems

  摘要：

  有机锡辅助的 C=N 双键与 2,4-戊二烯基和 α,β-不饱和酰基的三组分偶联，然后发生分子内 Diels-Alder 反应，导致 C=N 双键高度立体选择性双环化，从而在一烧瓶操作中得到烯丙基苄基和烯丙基育亨烷体系。

  DOI：

  10.1246/cl.1990.2161

文献信息

• Bicycloannulation of C=N Double Bonds through Organotin-Aided Three Component Coupling. A Short and Stereoselective Synthesis of (±)-<i>allo</i>-Berbane and (±)-<i>allo</i>-Yohimbane Systems
  作者：Ryohei Yamaguchi、Takashi Hamasaki、Kiitiro Utimoto、Sinpei Kozima、Hidemasa Takaya

  DOI：10.1246/cl.1990.2161

  日期：1990.12

  Organotin-aided three component couplings of C=N double bonds with 2,4-pentadienyl and α,β-unsaturated acyl groups followed by intramolecular Diels–Alder reactions result in highly stereoselective bicycloannulation of the C=N double bonds to afford allo-berbane and allo-yohimbane systems in one-flask operation.

  有机锡辅助的 C=N 双键与 2,4-戊二烯基和 α,β-不饱和酰基的三组分偶联，然后发生分子内 Diels-Alder 反应，导致 C=N 双键高度立体选择性双环化，从而在一烧瓶操作中得到烯丙基苄基和烯丙基育亨烷体系。
• A highly effective one-pot bicycloannulation methodology for the synthesis of berban and yohimban systems based on organotin-mediated three-component coupling (N-acylative pentadienylation of C:N bonds)
  作者：Ryohei Yamaguchi、Takashi Hamasaki、Tohru Sasaki、Tetsuo Ohta、Kiitiro Utimoto、Sinpei Kozima、Hidemasa Takaya

  DOI：10.1021/jo00057a028

  日期：1993.2

  A highly effective bicycloannulation methodology for the synthesis of berban and yohimban alkaloid systems is described. Three-component coupling reactions of 2,4-pentadienyltin reagents with C=N bonds and alpha,beta-unsaturated acyl chlorides furnish bicycloannulated products in a one-pot operation. For example, the reactions of 2,4-pentadienyltributyltin (1) with isoquinoline derivatives activated by acryloyl chloride afford the tetracyclic (+/-)-allo-berban systems stereoselectively. Similarly, the reaction of 1 with 3,4-dihydro-beta-carboline (11) gives the pentacyclic (+/-)-allo-yohimban system. The reaction is not affected by the stereochemistry of the 2,4-pentadienyltin reagent. A new substituted 2,4-pentadienyltin reagent, 3-(hydroxymethyl)-2,4-pentadienyltrimethyltin (19), is prepared via 3-(hydroxymethyl)pentadienyl dianion. The three-component coupling reaction of 19 with 11 and acryloyl chloride affords the (+/-)-allo-16-(hydroxymethyl)yohimban system, from which (+/-)-nitraraine is readily synthesized. In addition, 1,3-asymmetric induction leads to the high diastereoselectivity realized in bicycloannulation (up to 94% de) when (S)-3-[(tert-butyldimethylsiloxy)methyl]-3,4-dihydroisoquinoline (27), which is readily derived from L-phenylalanine, is used in the three-component coupling reaction.