(+/-)-alloyahimbane | 69349-93-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (+/-)-alloyahimbane
• 英文别名: (+/-)-alloyohimbane；(1S,15S,20S)-1,3,11,12,14,15,16,17,18,19,20,21-dodecahydroyohimban
• CAS: 69349-93-5
• 化学式: C₁₉H₂₄N₂
• 分子量: 280.413
• InChiKey: JUPDIHMJFPDGMY-IYOUNJFTSA-N

物化性质

• 熔点：
  143.5-144 °C
• 沸点：
  454.1±35.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  19
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-alloyahimbane 在 吡啶 、 乙酸酐 作用下， 生成 (+)-3-epi-allo-yohimban
  参考文献：
  名称：

  Chatterjee; Pakrashi, Journal of the Indian Chemical Society, 1959, vol. 36, p. 685,690

  摘要：

  DOI：
• 作为产物：
  描述：

  7-辛烯酸,甲基酯 在 镍 氢氧化钾 、 lithium aluminium tetrahydride 、 草酰氯 、 四溴化碳 、 N,N-二甲基甲酰胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 乙醇 、 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 4.0h， 生成 (+/-)-alloyahimbane
  参考文献：
  名称：

  A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems

  摘要：

  A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.

  DOI：

  10.1021/jo991742h

文献信息

• Enantioselective Syntheses of (-)-Alloyohimbane and (-)-Yohimbane by an Efficient Enzymatic Desymmetrization Process
  作者：Arun K. Ghosh、Anindya Sarkar

  DOI：10.1002/ejoc.201601171

  日期：2016.12

  Enantioselective syntheses of (-)-alloyohimbane and (-)-yohimbane was accomplished in a convergent manner. The key step involved a modified mild protocol for the enantioselective enzymatic desymmetrization of meso-diacetate. The protocol provided convenient access to an optically active monoacetate in multi-gram scale in high enantiomeric purity. This monoacetate was converted to (-)-alloyohimbane

  (-)-alloyohimbane 和 (-)-yohimbane 的对映选择性合成以收敛的方式完成。关键步骤涉及用于内消旋二乙酸酯的对映选择性酶促去对称化的改良温和方案。该协议提供了对高对映体纯度的多克级光学活性单乙酸酯的便捷访问。该单乙酸酯被转化为(-)-alloyohimbane。衍生醛的还原胺化导致异构化，产生反式产物，并允许合成 (-)-育亨宾。
• Short stereoselective synthesis of -alloyohimbane and -epialloyohimbane
  作者：Mauri Lounasmaa、Reija Jokela

  DOI：10.1016/s0040-4020(01)85442-9

  日期：1990.1

  A short and stereoselective synthesis for both -alloyohimbane and -epialloyohimbane using one and the same starting compound is presented.

  提出了使用一种和相同的起始化合物对α-金属环戊烷和-β-金属环戊烷进行短而立体的合成。
• A Concise, Enantioselective Approach for the Synthesis of Yohimbine Alkaloids
  作者：Eric R. Miller、M. Todd Hovey、Karl A. Scheidt

  DOI：10.1021/jacs.9b12319

  日期：2020.2.5

  We report a concise, enantioselective synthesis of the yohimbine alkaloids (-)-rauwolscine and (-)-alloyohimbane. The key transformation involves a highly enantio- and diastereoselective NHC-catalyzed dimerization and an amidation/N-acyliminium ion cyclization sequence to furnish four of the five requisite rings and three of the five stereocenters in two operations. This route also provides efficient

  我们报告了育亨宾生物碱 (-)-rauwolscine 和 (-)-alloyohimbane 的简明、对映选择性合成。关键转化涉及高度对映选择性和非对映选择性 NHC 催化的二聚化和酰胺化/N-酰基胺离子环化序列，以在两次操作中提供五个必需环中的四个和五个立体中心中的三个。该路线还提供了从常见中间体获得育亨宾生物碱核心立体三联体的所有四种非对映体排列的有效途径。这种平台方法与从卡宾催化反应中获取两种对映异构体的能力相结合，是一种强大的策略，可以为未来的生物医学研究生产各种复杂的生物碱和相关结构。
• Photocyclization of enamides. XXVI Photochemical synthesis of yohimban, epiyohimban, and alloyohimban, basic skeletal structures of yohimbine- and reserpine-type alkaloids.
  作者：TAKEAKI NAITO、OKIKO MIYATA、YUKIKO TADA、YOSHINO NISHIGUCHI、TOSHIKO KIGUCHI、ICHIYA NINOMIYA

  DOI：10.1248/cpb.34.4144

  日期：——

  Photocyclization of two enamides (2a and 2b) has provided a new entry for the construction of three yohimbans, yohimban (5a), epiyohimban (5b), and alloyohimban (5c), which are basic structures of yohimbine- and reserpine-type alkaloids.

  两个烯酰胺（2a 和 2b）的光环化为三个育亨班的构建提供了新的切入点，即育亨班（5a）、表育亨班（5b）和合金育亨班（5c），它们是育亨宾和间苯二酚类生物碱的基本结构。
• 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。