(1S,10bR)-8,9-dimethoxy-10b-(3-oxobutyl)-1-(triisopropylsilyloxy)-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-3-one | 950994-46-4

• 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: (1S,10bR)-8,9-dimethoxy-10b-(3-oxobutyl)-1-(triisopropylsilyloxy)-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-3-one
• 英文别名: (1S,10bR)-8,9-dimethoxy-10b-(3-oxobutyl)-1-tri(propan-2-yl)silyloxy-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-3-one
• CAS: 950994-46-4
• 化学式: C₂₇H₄₃NO₅Si
• 分子量: 489.728
• InChiKey: NJPAXIYIMZSWCB-AHKZPQOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.62
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1S,10bR)-8,9-dimethoxy-10b-(3-oxobutyl)-1-(triisopropylsilyloxy)-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-3-one 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以48%的产率得到(1S,10bR)-10b-(3-hydroxybutyl)-8,9-dimethoxy-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinolin-1-ol
  参考文献：
  名称：

  An enantiospecific synthesis of (+)-demethoxyerythratidinone from (S)-malic acid: key observations concerning the diastereocontrol in malic acid-derived N-acyliminium ion cyclisations

  摘要：

  The stereochemical outcome of N-acyliminium ion mediated cyclisations of malic acid derived lactams depend upon the nature of the protecting group on the lactam secondary alcohol, and also on the nature of the substituent at the reacting electrophilic centre. The origins of an unusual syn-selective cyclisation of a TIPS protected lactam are discussed, and the cyclisation is employed as the key step in an asymmetric synthesis of 3-demethoxyerythratidinone (4). (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.06.111
• 作为产物：
  描述：

  [(3S)-1-[2-(3,4-dimethoxyphenyl)ethyl]-2,5-dioxopyrrolidin-3-yl] acetate 在 2,6-二甲基吡啶 、 氧气 、 copper(l) chloride 、 palladium dichloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 生成 (1S,10bR)-8,9-dimethoxy-10b-(3-oxobutyl)-1-(triisopropylsilyloxy)-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinolin-3-one
  参考文献：
  名称：

  An enantiospecific synthesis of (+)-demethoxyerythratidinone from (S)-malic acid: key observations concerning the diastereocontrol in malic acid-derived N-acyliminium ion cyclisations

  摘要：

  The stereochemical outcome of N-acyliminium ion mediated cyclisations of malic acid derived lactams depend upon the nature of the protecting group on the lactam secondary alcohol, and also on the nature of the substituent at the reacting electrophilic centre. The origins of an unusual syn-selective cyclisation of a TIPS protected lactam are discussed, and the cyclisation is employed as the key step in an asymmetric synthesis of 3-demethoxyerythratidinone (4). (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.06.111

文献信息

• New approaches for the synthesis of erythrinan alkaloids
  作者：Fengzhi Zhang、Nigel S. Simpkins、Alexander J. Blake

  DOI：10.1039/b900189a

  日期：——

  A concise asymmetric total synthesis of (+)-erysotramidine is described, using chiral base desymmetrisation of a meso-imide, N-acyliminium addition, retro-Diels–Alder cycloaddition and radical cyclisation as the key steps. A related route, starting from a cyclobutene-fused imide, was explored, and established a novel construction of the Erythrina alkaloid skeleton using a key ring-opening/ring-closing

  描述了一个简明的不对称全合成（+）-异戊酰胺，使用内酰亚胺的手性碱去对称，N-酰基加成，Diels-Alder逆向加成和自由基环化为关键步骤。探索了一种从环丁烯稠合的酰亚胺开始的相关途径，并通过关键的开环/闭环复分解步骤建立了赤藓生物碱骨架的新型结构。除去不需要的乙烯基侧链的问题阻碍了该合成的完成。从开始，探索了到Erythrina系统的互补对映体专用路线。（L）-苹果酸。关于苹果酸衍生的N-酰基酰亚胺离子环化中的非对映异构控制，有一些出乎意料的观察，其中将醇官能团的保护基团从乙酸酯改变为OTIPS导致非对映异构的戏剧性变化。这些反应的产物可以通过自由基环化或分子内醛醇缩合反应作为关键步骤，转化为天然生物碱的已知中间体，并转化为（+）-脱甲氧基赤藓醇二酮本身。
• An enantiospecific synthesis of (+)-demethoxyerythratidinone from (S)-malic acid: key observations concerning the diastereocontrol in malic acid-derived N-acyliminium ion cyclisations
  作者：Fengzhi Zhang、Nigel S. Simpkins、Claire Wilson

  DOI：10.1016/j.tetlet.2007.06.111

  日期：2007.8

  The stereochemical outcome of N-acyliminium ion mediated cyclisations of malic acid derived lactams depend upon the nature of the protecting group on the lactam secondary alcohol, and also on the nature of the substituent at the reacting electrophilic centre. The origins of an unusual syn-selective cyclisation of a TIPS protected lactam are discussed, and the cyclisation is employed as the key step in an asymmetric synthesis of 3-demethoxyerythratidinone (4). (c) 2007 Elsevier Ltd. All rights reserved.