indoloquinolizidine | 10252-12-7

• 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: indoloquinolizidine
• 英文别名: (S)-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizine；(12bS)-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizine
• CAS: 10252-12-7
• 化学式: C₁₅H₁₈N₂
• 分子量: 226.321
• InChiKey: OURDZMSSMGUMKR-AWEZNQCLSA-N

物化性质

• 熔点：
  158-159 °C
• 沸点：
  397.5±32.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  indoloquinolizidine 在 sodium tetrahydroborate 、 sodium tungstate 、 双氧水 、 间氯过氧苯甲酸 、 三氟乙酸 作用下， 反应 2.25h， 生成
  参考文献：
  名称：

  Takayama, Hiromitsu; Seki, Norio; Kitajima, Mariko, Heterocycles, 1992, vol. 33, # 1, p. 121 - 125

  摘要：

  DOI：
• 作为产物：
  描述：

  1-甲基-4,9-二氢-3H-吡啶并[3,4-b]吲哚 在 lithium aluminium tetrahydride 、 W-2 Raney nickel 、 sodium cyanoborohydride 、 溶剂黄146 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 17.75h， 生成 indoloquinolizidine
  参考文献：
  名称：

  Stereoselective additions of chiral .alpha.-sulfinyl ketimine anions to ene esters. Asymmetric syntheses of indolo[2,3-a]quinolizidine and yohimban alkaloids

  摘要：

  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].

  DOI：

  10.1021/jo00025a011

文献信息

• A Highly Enantioselective Access to Tetrahydroisoquinoline and β-Carboline Alkaloids with Simple Noyori-Type Catalysts in Aqueous Media
  作者：Laurent Evanno、Joel Ormala、Petri M. Pihko

  DOI：10.1002/chem.200902289

  日期：2009.12.7

  enhancement: A very convenient modified protocol for the enantioselective transfer hydrogenation of dihydroisoquinoline skeletons under aqueous conditions is reported. Unmodified Noyori ligands can be used and the activity of the catalyst is greatly enhanced with silver additives (see scheme). The protocol was used in a very short synthesis of the alkaloids (S)‐harmicine and (S)‐crispine.

  增强银：报道了在水性条件下用于二氢异喹啉骨架的对映选择性转移氢化的非常方便的改进方案。可以使用未改性的Noyori配体，并且使用银添加剂可以大大提高催化剂的活性（参见方案）。该协议被用于非常短的生物碱（S）-甜菜碱和（S）-crispine的合成。
• Enantioselective Total Synthesis of Desbromoarborescidines A–C and the Formal Synthesis of (<i>S</i>)-Deplancheine
  作者：Pravat Mondal、Narshinha P. Argade

  DOI：10.1021/jo401079v

  日期：2013.7.5

  Starting from Boc-protected tryptamine and (S)-tetrahydro-5-oxo-2-furancarboxylic acid, facile enantioselective total synthesis of desbromoarborescidines A–C and the formal synthesis of (S)-deplancheine have been accomplished via a common intermediate (S)-indolo[2,3-a]quinolizine. Synthesis of enantiomerically pure (S)-acetoxyglutarimide, stereoselective reductive intramolecular cyclization, hydroxyl

  从Boc-保护的色胺和（起始小号） -四氢-5-氧代-2-呋喃甲酸，desbromoarborescidines A-C和（正式合成的容易对映选择性全合成小号）-deplancheine已经通过一个共同的中间体（已经完成小号）-吲哚并[2,3- a ]喹诺嗪。对映体纯的（S）-乙酰氧基戊二酰亚胺的合成，立体选择性还原分子内环化，羟基辅助的原位N -Boc脱保护，黄原酸酯的选择性脱氧和内酰胺水解，然后在分子内环化中适当交换氮区域选择性。决定性的步骤。
• MICROWAVE ASSISTED M<scp>c</scp>FADYEN–STEVENS AND HUANG–MINLON REACTIONS
  作者：Parasuraman Jaisankar、Bikash Pal、Venkatachalam Sesha Giri

  DOI：10.1081/scc-120005941

  日期：2002.1

  ABSTRACT Microwave irradiation has been employed in McFadyen–Stevens reaction to convert p-toluenesulfonyl hydrazides 1 to the aldehydes 2. Also, microwave has been applied in Huang–Minlon reduction of carbonyl compounds 3 to the corresponding hydrocarbons 4.

  摘要 微波辐射已被用于 McFadyen-Stevens 反应，以将对甲苯磺酰肼 1 转化为醛 2。此外，微波已被用于将羰基化合物 3 还原为相应的碳氢化合物 4。
• Enantioselective synthesis of some tetrahydroisoquinoline and tetrahydro-β-carboline alkaloids
  作者：Joanna Szawkało、Stefan J. Czarnocki、Anna Zawadzka、Krystyna Wojtasiewicz、Andrzej Leniewski、Jan K. Maurin、Zbigniew Czarnocki、Józef Drabowicz

  DOI：10.1016/j.tetasy.2007.01.014

  日期：2007.2

  Four alkaloids: (R)-(+)-cryspine A 5, (R)-(+)-octahydroindolo[2,3-a]quinolizidine 8, (R)-(+)-harmicine 19 and (R)-(+)-desbromoarborescidine 22 were prepared via the asymmetric transfer hydrogenation reaction of a prochiral enamine (iminium salt). The enantiomeric excesses of the isolated alkaloids were determined from their 1H NMR spectra measured in the presence of (+)-(R)-tert-butylphenylphosphinothio(seleno)ic

  四种生物碱：（R）-（+）-地平A 5，（R）-（+）-八氢吲哚并[2,3- a ]喹唑烷8，（R）-（+）-毒品19和（R）-（通过前手性烯胺（亚胺盐）的不对称转移氢化反应制备了+）-去溴阿糖胞苷22。根据在（+）-（R）-叔存在下测得的1 H NMR光谱确定分离出的生物碱的对映体过量-丁基苯基膦硫基（硒）酸作为手性溶剂。在所有情况下，通过X射线晶体学证实了新产生的立体碳原子上的绝对构型。
• New Procedure to Mask the 2,3-π Bond of the Indole Nucleus and Its Application to the Preparation of Potent Opioid Receptor Agonists with a Corynanthe Skeleton
  作者：Hiromitsu Takayama、Kaori Misawa、Naoki Okada、Hayato Ishikawa、Mariko Kitajima、Yoshio Hatori、Toshihiko Murayama、Sumphan Wongseripipatana、Kimihito Tashima、Kenjiro Matsumoto、Syunji Horie

  DOI：10.1021/ol062173k

  日期：2006.12.1

  Treatment of indole alkaloids with hypervalent iodine in the presence of ethylene glycol provides 2,3-ethylene glycol bridged adducts that could be converted into the original indoles under mild reductive conditions. This procedure, which involves masking of the reactivity of the indole nucleus at the beta-position, was utilized for the modification of the benzene ring of the indoline derivative and was

  在乙二醇存在下用高价碘处理吲哚生物碱可提供2,3-乙二醇桥接的加合物，可在温和的还原条件下将其转化为原始的吲哚。该方法涉及掩盖吲哚核在β位的反应性，该方法用于修饰吲哚啉衍生物的苯环，并用于制备具有Corynanthe骨架的有效的阿片受体激动剂。[反应：看文字]