(+)-(R)-1,2,3,4,6,7,12,12b-octahydro-4-oxoindolo<2,3-a>quinolizine | 137119-62-1

• 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: (+)-(R)-1,2,3,4,6,7,12,12b-octahydro-4-oxoindolo<2,3-a>quinolizine
• 英文别名: (R)-2,3,6,7,12,12b-hexahydroindolo[2,3-a]quinolizin-4(1H)-one；2,3,6,7,12,12b-hexahydro-1H-indolo[2,3-a]quinolizin-4-one；2,3,6,7,12,12b-hexahydroindolo[2,3-a]quinolizin-4(1H)-one；(+)-(R)-1,2,3,4,6,7,12,12b-octahydro-4-oxoindolo[2,3-a]quinolizine；(12bR)-2,3,6,7,12,12b-hexahydro-1H-indolo[2,3-a]quinolizin-4-one
• CAS: 137119-62-1
• 化学式: C₁₅H₁₆N₂O
• 分子量: 240.305
• InChiKey: RAWPBTDNWLONTE-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  36.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+)-(R)-1,2,3,4,6,7,12,12b-octahydro-4-oxoindolo<2,3-a>quinolizine 在 aluminum (III) chloride 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以94%的产率得到(R)-(+)-desbromoarborescidine A
  参考文献：
  名称：

  金催化的N-烯丙酰胺的不对称分子内环化反应，用于合成手性四烃基化合物

  摘要：

  顺应变化：利用PC-Phos配体实现了N-allenamides的高对映选择性金催化的分子内环化的第一个例子。该反应的实用性通过（R）-desbromoarborescidine A的全合成得到验证。

  DOI：

  10.1002/anie.201709595
• 作为产物：
  描述：

  (+)-(1S,12bS,SR)-1-<(4-methylphenyl)sulfinyl>-1,2,3,4,6,7,12,12b-octahydro-4-oxoindolo<2,3-a>quinolizine 在 W-2 Raney nickel 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 12.0h， 生成 (+)-(R)-1,2,3,4,6,7,12,12b-octahydro-4-oxoindolo<2,3-a>quinolizine
  参考文献：
  名称：

  Stereoselective addition reactions of chiral .alpha.-sulfinyl ketimine anions with ene esters. Facile asymmetric synthesis of indolo[2,3-a]quinolizidine and yohimbanoid alkaloids

  摘要：

  DOI：

  10.1021/jo00285a009

文献信息

• Unified Synthesis of Polycyclic Alkaloids by Complementary Carbonyl Activation**
  作者：Guoli He、Benjamin List、Mathias Christmann

  DOI：10.1002/anie.202102518

  日期：2021.6.7

  A complementary dual carbonyl activation strategy for the synthesis of polycyclic alkaloids has been developed. Successful applications include the synthesis of tetracyclic alkaloids harmalanine and harmalacinine, pentacyclic indoloquinolizidine alkaloid nortetoyobyrine, and octacyclic β-carboline alkaloid peganumine A. The latter synthesis features a protecting-group-free assembly and an asymmetric

  已经开发出用于合成多环生物碱的互补双羰基活化策略。成功的应用包括四环生物碱骆驼蓬菌素和骆驼蓬菌素、五环吲哚喹啉西啶生物碱去甲代拜林和八环β-咔啉生物碱peganumine A的合成。后者的合成具有无保护基组装和不对称二磺酰亚胺催化环化的特点。此外，还实现了 hirsutine、deplancheine、10-desbromoarborescidine A 和 oxindole 生物碱钩藤碱和异钩藤碱的正式合成。最终完成了小檗碱生物碱ilicifoline B的简捷合成。
• Novel Supramolecular Palladium Catalyst for the Asymmetric Reduction of Imines in Aqueous Media
  作者：Wender A. da Silva、Manoel T. Rodrigues、N. Shankaraiah、Renan B. Ferreira、Carlos Kleber Z. Andrade、Ronaldo A. Pilli、Leonardo S. Santos

  DOI：10.1021/ol9011772

  日期：2009.8.6

  A novel approach to the asymmetric reduction of dihydro-β-carboline derivatives to the corresponding tetrahydro-β-carbolines is described based on the supramolecular lyophilized complex formed from β-cyclodextrin/imines as an enzyme mimetic and palladium hydride as the reducing agent. The methodology allowed us to develop a short and efficient preparation of (R)-harmicine and (R)-deplancheine alkaloids

  基于由β-环糊精/亚胺作为酶模拟物和氢化钯作为还原剂形成的超分子冻干复合物，描述了一种将二氢-β-咔啉衍生物不对称还原为相应的四氢-β-咔啉的新方法。该方法使我们能够开发出一种短而有效的（R）-甜菜碱和（R）-十倍体碱生物碱的制备方法，分别具有89％和90％的高总收率和ee。
• Enantioselective Pictet−Spengler-Type Cyclizations of Hydroxylactams:  H-Bond Donor Catalysis by Anion Binding
  作者：Izzat T. Raheem、Parvinder S. Thiara、Emily A. Peterson、Eric N. Jacobsen

  DOI：10.1021/ja076179w

  日期：2007.11.1

  indolizinone and quinolizinone products are obtained in the thiourea-catalyzed cyclization of tryptamine-derived hydroxylactams. Substituent and counterion effect studies point to a novel mechanism of catalysis involving rate-limiting anion abstraction and binding by the thiourea.

  在硫脲催化的色胺衍生的羟基内酰胺的环化中获得高度对映体富集的吲哚嗪酮和喹嗪酮产物。取代基和反离子效应研究指出了一种新的催化机制，涉及限速阴离子提取和硫脲结合。
• Stereoselective additions of chiral .alpha.-sulfinyl ketimine anions to ene esters. Asymmetric syntheses of indolo[2,3-a]quinolizidine and yohimban alkaloids
  作者：Duy H. Hua、S. Narasimha Bharathi、Jagath A. K. Panangadan、Atsuko Tsujimoto

  DOI：10.1021/jo00025a011

  日期：1991.12

  The in-situ 1,4-addition/ring-closure reactions of chiral alpha-sulfinyl ketimine anions with acyclic and cyclic ene esters offer a simple, convenient route for the construction of chiral cyclic alkaloids having a nitrogen-atom ring juncture. Asymmetric induction in the conjugate-addition reaction of the carbanions derived from alpha-sulfinyl ketimines possessing chiral sulfur with various cyclic and acyclic ene esters, subsequent ring-closure reaction, and reduction of the resulting beta-sulfinyl enamides were utilized in the syntheses of (-)-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a] quinolizine [(-)-1], (-)-alloyohimban [(-)-2], (+)-3-epi-alloyohimban [(+)-3], and (-)-yohimban [(-)-4].
• Antiproliferative activity of arborescidine alkaloids and derivatives
  作者：Leonardo S. Santos、Cristina Theoduloz、Ronaldo A. Pilli、Jaime Rodriguez

  DOI：10.1016/j.ejmech.2009.04.005

  日期：2009.9

  Current issues in cancer research involve searching for novel anticancer compounds that can be used to regulate the cell cycle and lead to more effective treatments of tumors. In this study, it was hypothesized that possessing a cyclic alkaloid similar to harmine, arborescidines can disrupt the proliferative state of cancer cells and block the activity of topoisomerases. The antiproliferative activity of arborescidines A-C and their derivatives was evaluated in vitro against four human tumor cell lines: gastric adenocarcinoma, lung cancer, bladder carcinoma and leukemia. Assuming the mechanism of action by topoisomerase II binding model, the compounds possessing the greatest activity had nonpolar side-chain into hydrophobic binding region on the DNA/topo II complex. (C) 2009 Elsevier Masson SAS. All rights reserved.