(+)-cryptaustoline | 133320-20-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: (+)-cryptaustoline
• 英文别名: (7R,12aS)-3,9,10-trimethoxy-7-methyl-5,6,12,12a-tetrahydroindolo[2,1-a]isoquinolin-7-ium-2-ol;iodide
• CAS: 133320-20-4
• 化学式: C₂₀H₂₄NO₄*I
• 分子量: 469.319
• InChiKey: PKTJQENFLPKCOB-ZOEDVAEJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.21
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1-(溴甲基)-2-氯-4,5-二甲氧基苯 在 仲丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 188.17h， 生成 (+)-cryptaustoline
  参考文献：
  名称：

  Formamidines in synthesis. An efficient one-pot synthesis of 7-substituted indolines via intramolecular cyclization of (2-phenethyl)formamidines. An asymmetric route to benzopyrrocoline alkaloids

  摘要：

  o-Chloro-beta-phenethylamines, transformed into the N-tert-butylformamidines, were found to be excellent precursors to indolines following benzyne formation. A series of methoxy-substituted o-chlorophenethylamines containing an N-alkyl or aryl substitutent were subjected to sec-butyllithium producing the ortho-lithiated aromatic which subsequently lost lithium chloride at temperatures ranging from -78 to -50-degrees-C. The resulting benzyne was intramolecularly trapped providing the titled heterocycles. Quenching the reaction resulted in elimination of the tert-butyl isocyanide (isolated after aqueous workup as tert-butylformamide) and protonation (or alkylation) of the 7-lithio position. Overall the yields for this process were 60-95% for a variety of N-substituted phenethylamines. In addition, a one-pot total asymmetric route to benzopyrrocoline alkaloids was featured using this benzyne trapping of chiral formamidines.

  DOI：

  10.1021/jo00039a029

文献信息

• (-)-Cryptaustoline: its synthesis, revision of absolute stereochemistry, and mechanism of inversion of stereochemistry
  作者：A. I. Meyers、Thais M. Sielecki、Debbie C. Crans、Robert W. Marshman、Thanh H. Nguyen

  DOI：10.1021/ja00048a020

  日期：1992.10

  The asymmetric synthesis of (S)-(+)-cryptaustoline was accomplished and found to differ in sign of rotation with the natural «S»-(-)-material. The previously assigned absolute configuration was found to be incorrect and is now corrected. The reversal in stereochemistry came about through an unusual manner involving (S)-(+)-laudanosoline (3) cyclizing to (R)-(-)-cryptaustoline ((-)-1c). The mechanism

  完成了 (S)-(+)-cryptaustoline 的不对称合成，发现其旋转符号与天然 «S»-(-)-材料不同。发现先前分配的绝对配置不正确，现在已更正。立体化学的逆转是通过一种不寻常的方式实现的，包括 (S)-(+)-laudanosoline (3) 环化为 (R)-(-)-cryptaustoline ((-)-1c)。通过氧化一系列月桂醇油碱的氘代衍生物来探索该机制，所有这些衍生物都在所得的隐孢子碱中保留了氘
• Total synthesis of the dibenzopyrrocoline alkaloid S-(+)-cryptaustoline. Revision of absolute configuration due to an unusual inversion in stereochemistry
  作者：A. I. Meyers、Thais M. Sielecki

  DOI：10.1021/ja00007a084

  日期：1991.3

  The natural alkaloid cryptaustoline is (13R,7S)-(−)-1 due to the heretofore unprecedented inversion while the formamidine route led to the expected (13S,7R)-(+)-1

  由于迄今为止前所未有的反转，天然生物碱 cryptaustoline 是 (13R,7S)-(-)-1，而甲脒途径导致预期的 (13S,7R)-(+)-1
• YASUDA, SHINGO;HIRASAWA, TAEKO;YOSHIDA, SHUJI;HANAOKA, MIYOJI, CHEM. AND PHARM. BULL., 37,(1989) N, C. 1682-1683
  作者：YASUDA, SHINGO、HIRASAWA, TAEKO、YOSHIDA, SHUJI、HANAOKA, MIYOJI

  DOI：——

  日期：——
• METHOD FOR EXTRACTING TARGET ALKALOID USING AN IONIC LIQUID AS EXTRACTING SOLVENT
  申请人：Bioniqs Limited

  公开号：EP2001877A1

  公开（公告）日：2008-12-17
• [EN] METHOD FOR EXTRACTING TARGET ALKALOID USING AN IONIC LIQUID AS EXTRACTING SOLVENT<br/>[FR] PROCÉDÉ D'EXTRACTION D'UN ALCALOÏDE CIBLE FAISANT APPEL À UN LIQUIDE IONIQUE COMME SOLVANT D'EXTRACTION
  申请人：BIONIQS LTD

  公开号：WO2007110637A1

  公开（公告）日：2007-10-04

  [EN] Method for extracting a target alkaloid from a mixture of species, typically from plant matter, using an ionic liquid as an extracting solvent. The ionic liquid may in particular be an alkanolyl-, alkoxyalkyl- or aminoalkyl-substituted ammonium salt.
  [FR] L'invention concerne un procédé d'extraction d'un alcaloïde cible à partir d'un mélange d'espèces, généralement d'un matériau végétal, en utilisant un liquide ionique en tant que solvant d'extraction. Le liquide ionique peut notamment être un sel d'ammonium substitué par un alcanoyle, un alcoxyalkyle ou un aminoalkyle.