(1S,2R,10bS)-2-(tert-butyldimethylsilanyloxy)-1-hydroxy-8,9-dimethoxy-10b-phenylethynyl-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinolin-3-one | 749922-72-3

• 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: (1S,2R,10bS)-2-(tert-butyldimethylsilanyloxy)-1-hydroxy-8,9-dimethoxy-10b-phenylethynyl-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinolin-3-one
• 英文别名: (1S,2R,10bS)-2-[tert-butyl(dimethyl)silyl]oxy-1-hydroxy-8,9-dimethoxy-10b-(2-phenylethynyl)-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-3-one
• CAS: 749922-72-3
• 化学式: C₂₈H₃₅NO₅Si
• 分子量: 493.675
• InChiKey: BQTOWSWYGUZDGX-SKVJQKLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  68.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1S,2R,10bS)-2-(tert-butyldimethylsilanyloxy)-1-hydroxy-8,9-dimethoxy-10b-phenylethynyl-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinolin-3-one 在 氟化氢吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 (1S,2R,10bS)-1,2-dihydroxy-8,9-dimethoxy-10b-(2-phenylethynyl)-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-3-one
  参考文献：
  名称：

  具有季碳立体中心的光学纯的高度官能化的四氢异喹啉的新途径

  摘要：

  描述了具有季碳立构中心的高度取代的光学纯的四氢异喹啉的简便合成方法。1,2-二羟基-六氢-吡咯并-异喹啉1的乙醇裂解提供了环状半缩醛的混合物，可以通过分子内化学选择性Cannizzaro反应将其转化为相应的β-氨基醇，而IBX氧化则得到N-甲酰基醛。我们已经通过合成（+）-6,7-二甲氧基-salsoline-1-羧酸及其新的1-苯基类似物证明了这种合成子的实用性。

  DOI：

  10.1016/j.tet.2008.01.011
• 作为产物：
  描述：

  magnesium,ethynylbenzene,bromide 在 咪唑 、 4-二甲氨基吡啶 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 24.0h， 生成 (1S,2R,10bS)-2-(tert-butyldimethylsilanyloxy)-1-hydroxy-8,9-dimethoxy-10b-phenylethynyl-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinolin-3-one
  参考文献：
  名称：

  Diastereoselective synthesis of 10b-substituted hexahydropyrroloisoquinolines from l-tartaric acid. Creation of a quaternary carbon stereocentre via N-acyliminium ion cyclization

  摘要：

  A simple, three-step synthesis of 10b-substituted-hexahydropyrroloisoquinolines 12-17 starting from an L-tartaric acid derived imide is described. The methodology presented employs the addition of a Grignard reagent to the imide carbonyl group, followed by a one-pot acetylation-cyclization sequence. The crucial step, an acid-catalyzed carbon-carbon bond forming reaction via an N-acyliminium ion offers moderate to high stereoselectivity, which has been shown to be strongly dependent on the size of the R-substituent. The mixtures of pyrroloisoquinolines obtained can be separated as enantiomerically pure 2-silyloxy-derivatives. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.06.036

文献信息

• 10b-Substituted hexahydropyrrolo-isoquinolines: studies on diastereoselective formation of a quaternary carbon stereocenter via N-acyliminium ion cyclization
  作者：Zbigniew Kałuża、Danuta Mostowicz、Grzegorz Dołęga、Katarzyna Mroczko、Robert Wójcik

  DOI：10.1016/j.tet.2005.10.028

  日期：2006.1

  The stereoselective synthesis of hexahydro-pyrroloisoquinolines with a quaternary carbon stereocenter is described. The presented methodology employs the addition of a Grignard reagent to the carbonyl group of imide 1, derived from l-tartaric acid, followed by acetylation and BF3·Et2O induced cyclization. The acetylation–cyclization sequence can be run either as a one-pot process, or stepwise in a

  描述了具有季碳立体中心的六氢-吡咯并异喹啉的立体选择性合成。所提出的方法采用了将格氏试剂添加到衍生自1-酒石酸的酰亚胺1的羰基上，然后进行乙酰化和BF 3 ·Et 2 O诱导的环化。乙酰化-环化顺序既可以一锅法进行，也可以在选定的溶剂中逐步进行。关键步骤是通过N-酰亚胺离子进行酸催化的碳-碳键形成反应，可提供高的立体选择性，这已证明与R 1的大小密切相关。取代基和反应条件，即溶剂的选择，路易斯酸的量，温度和底物的浓度。基于观察到的结果，提出了经由N-酰基亚胺阳离子参与溶剂的环化。
• A new route to optically pure highly functionalized tetrahydro-isoquinolines with a quaternary carbon stereocenter
  作者：Zbigniew Kałuża、Danuta Mostowicz、Grzegorz Dołęga、Robert Wójcik

  DOI：10.1016/j.tet.2008.01.011

  日期：2008.3

  A facile synthesis of highly substituted, optically pure tetrahydro-isoquinolines with a quaternary carbon stereocenter is described. Glycolic cleavage of 1,2-dihydroxy-hexahydro-pyrrolo-isoquinolines 1 affords a mixture of cyclic hemiacetals, which can be converted via intramolecular chemoselective Cannizzaro reaction into respective β-amino alcohols, whereas the IBX oxidation gives N-formyl aldehydes

  描述了具有季碳立构中心的高度取代的光学纯的四氢异喹啉的简便合成方法。1,2-二羟基-六氢-吡咯并-异喹啉1的乙醇裂解提供了环状半缩醛的混合物，可以通过分子内化学选择性Cannizzaro反应将其转化为相应的β-氨基醇，而IBX氧化则得到N-甲酰基醛。我们已经通过合成（+）-6,7-二甲氧基-salsoline-1-羧酸及其新的1-苯基类似物证明了这种合成子的实用性。
• Diastereoselective synthesis of 10b-substituted hexahydropyrroloisoquinolines from l-tartaric acid. Creation of a quaternary carbon stereocentre via N-acyliminium ion cyclization
  作者：Danuta Mostowicz、Robert Wójcik、Grzegorz Dołęga、Zbigniew Kałuża

  DOI：10.1016/j.tetlet.2004.06.036

  日期：2004.7

  A simple, three-step synthesis of 10b-substituted-hexahydropyrroloisoquinolines 12-17 starting from an L-tartaric acid derived imide is described. The methodology presented employs the addition of a Grignard reagent to the imide carbonyl group, followed by a one-pot acetylation-cyclization sequence. The crucial step, an acid-catalyzed carbon-carbon bond forming reaction via an N-acyliminium ion offers moderate to high stereoselectivity, which has been shown to be strongly dependent on the size of the R-substituent. The mixtures of pyrroloisoquinolines obtained can be separated as enantiomerically pure 2-silyloxy-derivatives. (C) 2004 Elsevier Ltd. All rights reserved.