(+/-)-(1R,9aS)-octahydro-2H-quinolizin-1-amine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: (+/-)-(1R,9aS)-octahydro-2H-quinolizin-1-amine
• 英文别名: octahydro-quinolizin-1-ylamine；1-aminoquinolizidine；(1S,9aR)-2,3,4,6,7,8,9,9a-octahydro-1H-quinolizin-1-amine
• 化学式: C₉H₁₈N₂
• 分子量: 154.255
• InChiKey: SHDAASRRPFQHIB-DTWKUNHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-(1R,9aS)-octahydro-2H-quinolizin-1-amine 、 乙酰氯 在 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以72%的产率得到(+/-)-Epiquinamide
  参考文献：
  名称：

  A concise synthesis of (±) and a total synthesis of (+)-epiquinamide

  摘要：

  A total synthesis of the quinolizidine alkaloid (+)-epiquinamide 1 has been achieved starting from (-)-pipecolinic acid 3. The key step is the highly diastereoselective addition of a TBDMS-protected propargyl alcohol to a chiral aldehyde derived from 3 to give erythro alkynol 19, which is then easily transformed into the desired bicyclic skeleton. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.05.092
• 作为产物：
  描述：

  hexahydro-quinolizin-1-one 在 吡啶 、 lithium aluminium tetrahydride 、 盐酸羟胺 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 2.0h， 生成 (+/-)-(1R,9aS)-octahydro-2H-quinolizin-1-amine
  参考文献：
  名称：

  A concise synthesis of (±) and a total synthesis of (+)-epiquinamide

  摘要：

  A total synthesis of the quinolizidine alkaloid (+)-epiquinamide 1 has been achieved starting from (-)-pipecolinic acid 3. The key step is the highly diastereoselective addition of a TBDMS-protected propargyl alcohol to a chiral aldehyde derived from 3 to give erythro alkynol 19, which is then easily transformed into the desired bicyclic skeleton. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.05.092

文献信息

• Organocatalytic enantioselective synthesis of quinolizidine alkaloids (+)-myrtine, (−)-lupinine, and (+)-epiepiquinamide
  作者：Santos Fustero、Javier Moscardó、María Sánchez-Roselló、Sonia Flores、Marta Guerola、Carlos del Pozo

  DOI：10.1016/j.tet.2011.07.017

  日期：2011.9

  quinolizidine alkaloids (+)-myrtine, (−)-lupinine, and (+)-epiepiquinamide is described. It involved, as the key step, an enantioselective intramolecular aza-Michael reaction (IMAMR) catalyzed by Jørgensen catalyst I, affording the common precursor with high enantioselectivity. This compound was subsequently transformed into the three alkaloids in a highly diastereoselective manner.

  描述了喹唑烷生物碱（+）-美金汀，（-）-羽扇豆碱和（+）-表位表喹酰胺的有机催化合成。作为关键步骤，它涉及由约根森催化剂I催化的对映选择性分子内aza-Michael反应（IMAMR），从而提供具有高对映选择性的常见前体。该化合物随后以高度非对映选择性的方式转化为三种生物碱。
• Reductive transformations of unsaturated azabicyclic nitrolactams
  作者：Mihály Viktor Pilipecz、Tamás Róbert Varga、Pál Scheiber、Zoltán Mucsi、Amélie Fàvre-Mourgues、Sándor Boros、László Balázs、Gábor Tóth、Péter Nemes

  DOI：10.1016/j.tet.2012.04.100

  日期：2012.7

  different reducing methods unsaturated indolizidine and quinolizidine lactams substituted with a nitro group were transformed into various alkaloid-like derivatives. Hydrogen transfer and palladium catalyzed hydrogenation gave compounds of ketolactam or lactam type meanwhile the nitro group was eliminated. On the other hand, in presence of Raney-nickel catalyst the nitro compounds were reduced to diastereomeric

  使用不同的还原方法，将被硝基取代的不饱和吲哚并咪唑和喹唑并内酰胺转化为各种生物碱样衍生物。氢转移和钯催化的氢化得到酮内酰胺或内酰胺类型的化合物，同时消除了硝基。另一方面，在阮内镍催化剂的存在下，硝基化合物被还原为非对映异构的氨基衍生物，其立体化学通过NMR光谱法得以阐明。使用双二甲氧基乙氧基氢化铝钠（Red-Al）作为还原剂，分离并表征了意外的三环氮杂环丁烷。
• Electroreductive intramolecular coupling of aliphatic cyclic imides with ketones and O-methyloximes
  作者：Naoki Kise、Kazuaki Fukazawa、Toshihiko Sakurai

  DOI：10.1016/j.tetlet.2010.08.081

  日期：2010.11

  The electroreductive intramolecular coupling of aliphatic cyclic imides with ketones in isopropanol gave five- and six-membered cyclized products. Similarly, the electroreductive intramolecular coupling of aliphatic cyclic imides with O-methyloximes afforded five-, six-, and seven-membered cyclized products. These reactions provide a useful method to synthesize azabicyclo[n.m.0] compounds. The bicyclic

  脂肪环酰亚胺与酮在异丙醇中的电还原分子内偶联产生五元和六元环化产物。类似地，脂族环状酰亚胺与O-甲基肟的电还原分子内偶联提供了五元，六元和七元环化产物。这些反应提供了合成氮杂双环[nm0]化合物的有用方法。通过用NaB（CN）H 3或Et 3 SiH / BF 3 ·Et 2 O还原，将双环产物立体选择性地转化为相应的脱氧化合物。
• Epiquinamide: A Poison That Wasn’t from a Frog That Was
  作者：Richard W. Fitch、Gordon D. Sturgeon、Shaun R. Patel、Thomas F. Spande、H. Martin Garraffo、John W. Daly、Richard H. Blaauw

  DOI：10.1021/np8005452

  日期：2009.2.27

  In 2003, we reported the isolation, structure elucidation, and pharmacology of epiquinamide (1), a novel alkaloid isolated from an Ecuadoran poison frog, Epipedobates tricolor. Since then, several groups, including ours, have undertaken synthetic efforts to produce this compound, which appeared initially to be a novel, beta 2-selective nicotinic acetylcholine receptor agonist. Based on prior chiral GC analysis of synthetic and natural samples, the absolute structure of this alkaloid was established as (1S,9aS)-1-acetamidoquinolizidine. We have synthesized the (1R*,9aS*)-isomer (epi-epiquinamide) using an iminium ion nitroaldol reaction as the key step. We have also synthesized ent-1 semisynthetically from (-)-lupinine. Synthetic epiquinamide is inactive at nicotinic receptors, in accord with recently published reports. We have determined that the activity initially reported is due to cross-contamination from co-occurring epibatidine in the isolated material.
• The synthesis and nicotinic binding activity of (±)-epiquinamide and (±)-C(1)-epiepiquinamide
  作者：Akira Kanakubo、Diane Gray、Neal Innocent、Susan Wonnacott、Timothy Gallagher

  DOI：10.1016/j.bmcl.2006.05.100

  日期：2006.9

  The synthesis of (+/-)-epiquinamide 1 and (+/-)-C(1)-epiepiquinamide 2 based on the use of a Curtius rearrangement to introduce the C(1) amino residue is reported. In a competition binding assay for [H-3]epibatidine binding to rat brain membranes neither (+/-)-1 nor (+/-)-2 showed any significant level of nicotinic activity. (c) 2006 Elsevier Ltd. All rights reserved.