1-表羽扇豆碱 | 486-71-5

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 羽扇豆生物碱
• 中文名称: 1-表羽扇豆碱
• 英文名称: (+)-epilupinine
• 英文别名: 1-Epilupinine；[(1S,9aR)-2,3,4,6,7,8,9,9a-octahydro-1H-quinolizin-1-yl]methanol
• CAS: 486-71-5
• 化学式: C₁₀H₁₉NO
• 分子量: 169.267
• InChiKey: HDVAWXXJVMJBAR-NXEZZACHSA-N

物化性质

• 熔点：
  77-78 °C
• 沸点：
  245.0±13.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-表羽扇豆碱 在 氯化亚砜 作用下， 以 乙醚 、 二甲基亚砜 为溶剂， 反应 24.0h， 生成 epi-lupinylphenylketone
  参考文献：
  名称：

  2-Phenyl-3-(quinolizidin-1-yl)-5-substituted indoles as platelet antiaggregating agents

  摘要：

  A set of ten 2-phenyl-3-(quinolizidin-1-yl)-5-substituted indoles was prepared through the Fischer cyclization of lupinyl- and epi-lupinylphenylketone 4-substituted phenylhydrazones. Compounds were tested for antiaggregating activity on human platelets activated by adenosine diphosphate (ADP), collagen and adrenaline. At 2.5 x 10(-4) M concentration most compounds strongly inhibited the aggregation induced by all the agonists considered and many of them still displayed good activity at 0.625 x 10(-4) M concentration. The least active (1c) and one of the most active (1d) compounds were also tested for antiaggregating activity on rabbit platelets activated by ADP, PAF and sodium arachidonate. Both the compounds were active against ADP and PAF, but only 1d inhibited the arachidonate-induced aggregation (100% at 8 x 10(-6) M concentration) and increased the bleeding time in mice. The same compounds were subjected to a general pharmacological screening and found to display several activities; of particular interest was the dose dependent reduction of serum cholesterol and heparin precipitating betalipoproteins in hypercholesterolemic mice exerted by 1c, which was still significant at the oral dose of 10 mg/kg.

  DOI：

  10.1016/j.farmac.2003.11.009
• 作为产物：
  描述：

  哌啶酮 在 镍 lithium aluminium tetrahydride 、 三氟化硼乙醚 、 四丁基溴化铵 、 氢气 、 sodium hydride 、 三乙胺 、 sodium iodide 作用下， 以 乙醚 、 乙醇 、 乙腈 为溶剂， 25.0~200.0 ℃ 、15.2 MPa 条件下， 反应 77.0h， 生成 1-表羽扇豆碱
  参考文献：
  名称：

  β-Enaminoestersbicycliques：合成及还原立体异构体。加入异维他命醇，曲沙米啶，羽扇豆碱等

  摘要：

  官能化的N-烷基-β-烯胺酸酯是氮桥双环β-烯胺酸酯的前体。通过β-烯氨基酯的分子内烷基化或通过β-烯氨基酯的热解来制备化合物。化合物的立体特异性还原热控制引线下双环β氨基酯，，或它们是天然氨基醇等lupinine的良好前体或isoretronecanol 。

  DOI：

  10.1016/s0040-4020(01)85128-0

文献信息

• An unexpected reversal in the stereochemistry of transannular cyclizations. A stereoselective synthesis of (±)-epilupinine.
  作者：Eric D. Edstrom

  DOI：10.1016/s0040-4039(00)93536-6

  日期：1991.10

  The transannular cyclizations of N-benzylhexahydroazec-5-en-2-one and N-benzylhexahydroazon-5-en-2-one using iodine or phenylselenenyl bromide affords substituted quinolizidines and indolizidines, respectively. In the case of the ten-membered ring lactams an unexpected reversal in stereochemistry was observed. These results were confirmed by elaboration of the iodo cycloadduct 4a into (±)-epilupinine

  使用碘或苯基硒烯基溴化物对N-苄基六氢氮杂-5-烯-2-酮和N-苄基六氢氮杂-5-烯-2-酮进行环环形环化，分别得到取代的喹啶和吲哚并咪唑。在十元环内酰胺的情况下，观察到立体化学的出乎意料的逆转。这些结果通过将碘代环加合物4a加工成（±）-癫痫素而得以证实。
• Organocatalytic Asymmetric Mannich Cyclization of Hydroxylactams with Acetals: Total Syntheses of (−)-Epilupinine, (−)-Tashiromine, and (−)-Trachelanthamidine
  作者：Dipankar Koley、Yarkali Krishna、Kyatham Srinivas、Afsar Ali Khan、Ruchir Kant

  DOI：10.1002/anie.201407185

  日期：2014.11.24

  cyclization between a hydroxylactam and acetal is described to provide fused, bicyclic alkaloids bearing a bridgehead N atom. Both aliphatic and aromatic substrates were used in this transformation to furnish chiral pyrrolizidinone, indolizidinone, and quinolizidinone derivatives in up to 89 % yield and 97 % ee. The total syntheses of (−)‐epilupinine, (−)‐tashiromine, and (−)‐trachelanthamidine also

  羟基内酰胺和乙缩醛之间的不对称有机催化单锅曼尼希环化反应可提供带有桥头N原子的稠合双环生物碱。脂肪族和芳香族底物均用于该转化中，以高达89％的收率和97％的ee值提供手性吡咯烷酮，吲哚啶酮和喹喔啉酮衍生物。（-）-癫痫素，（-）-tashiromine和（-）-trachelanthamidine的总合成也证明了该方法的普遍性。
• Microwave-Assisted Domino Hydroformylation/Cyclization Reactions: Scope and Limitations
  作者：André Mann、Maurizio Taddei、Etienne Airiau、Claire Chemin、Nicolas Girard、Giacomo Lonzi、Elena Petricci、Jessica Salvadori

  DOI：10.1055/s-0030-1258207

  日期：2010.9

  reported to illustrate each sequence. Although apparently more versatile, hydroformylation of alkenes using MW heating is sensitive to the nature of the nucleophiles present in the substrates, evidencing that the conventional heating process cannot be completely replaced by MW irradiation. domino reaction - heterocycles - nucleophilic addition - cyclization - hemiacetals - Pictet-Spengler reaction

  烯烃的加氢甲酰化反应可以在微波（MW）介电加热下，在短时间内以低合成气压力进行。带有O，N或C亲核片段的烯烃可以设计用于多米诺反应，主要是环缩合反应。烯丙醇和高烯丙基醇是在MW加热下环化加氢甲酰化为乳糖醇的优良底物。在NaOAc作为另外的亲核试剂的存在下，发生多米诺反应，产生2-乙酰氧基四氢呋喃，适合通过氧碳through离子将C-亲核试剂引入四氢呋喃环上。申请描述了环巴胺的呋喃并哌啶亚结构的合成。使用烯烃酰胺时，多米诺过程崩溃为一个瞬时的酰基酰亚胺离子，该离子进一步与其他C-亲核试剂环合。为了进行多米诺加氢甲酰化Pictet-Spengler或Aza-Sakurai反应，传统加热条件下的高压釜是必不可少的。据报道，（±）-癫痫碱和高丝氨酸碱生物碱的合成说明了每个序列。尽管显然更通用，但是使用MW加热的烯烃加氢甲酰化反应对底物中存在的亲核试剂的性质敏感，证明常规的加热过程不能完全被MW辐射所代替。
• Iminium ion cascade reactions: stereoselective synthesis of quinolizidines and indolizidines
  作者：Shawn M. Amorde、Ivan T. Jewett、Stephen F. Martin

  DOI：10.1016/j.tet.2008.10.074

  日期：2009.4

  A novel iminium ion cascade reaction has been developed that allows for the stereoselective synthesis of a variety of substituted aza-fused bicycles. The combination of amino allylsilanes and aldehydes (or ketones) was used to synthesize a number of quinolizidines and indolizidines in a one-pot reaction sequence. This technology has been used to effect the facile syntheses of several indolizidine and

  已经开发了一种新型亚胺离子级联反应，可以立体选择性地合成各种取代的氮杂融合双环。氨基烯丙基硅烷和醛（或酮）的组合被用于在一锅反应序列中合成许多喹唑西啶和吲哚里西啶。该技术已被用于实现几种吲哚里西啶和喹诺西啶天然产物的简便合成，包括 (±)-epilupinine、(±)-tashiromine 和 (-)-epimyrtine。已经检查了底物范围，改变氨基烯丙基硅烷（伯、仲和共轭）和羰基化合物（醛和酮）的类型，以提供各种稠环结构。改变选择的组分允许在核心结构的不同位置包含合成有用的官能团。
• Furan-Terminated <i>N</i>-Acyliminium Ion Initiated Cyclizations in Alkaloid Synthesis
  作者：Steven P. Tanis、Melissa V. Deaton、Lisa A. Dixon、Mark C. McMills、Jeffrey W. Raggon、Mark A. Collins

  DOI：10.1021/jo980718l

  日期：1998.10.1

  cyclizations for the synthesis of linearly fused alkaloid precursors (Figure 2) is presented. The outcome of the cyclization event depends on the position of furan tether attachment (2 vs 3), tether length, and furan 5-substituent (R = H, CH(3), Ar). 3-Substituted furans cyclized to form 6- and 7-membered ring containing furans 35-38, 50, and 51 in good to excellent yields. 2-Substituted furans closed to form

  提出了呋喃封端的N-酰基酰亚胺离子引发的环化用于线性融合生物碱前体合成的实用性的研究（图2）。环化事件的结果取决于呋喃系链连接的位置（2比3），系链长度和呋喃5取代基（R = H，CH（3），Ar）。3-取代的呋喃环化形成具有良好或优异收率的含呋喃35-38、50和51的6和7元环。2个取代的呋喃闭合，仅形成6元环；然而，所得产物是呋喃5-取代基的函数。5-H呋喃17和18仅产生相应的呋喃21和22，而5-CH（3）-呋喃42和43仅产生含二酮的化合物44和45。5-芳基呋喃66-71提供了呋喃的混合物-含二酮的产品72-83，其比例与苯基部分的取代有关。还讨论了表卢皮碱10的制备。