diethyl (4aS,5S,8S,13bR)-5-hydroxy-11,12-dimethoxy-6-oxospiro[1,2,4,5,8,9-hexahydroindolo[7a,1-a]isoquinoline-3,2'-1,3-dioxolane]-4a,8-dicarboxylate | 157007-23-3

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 刺桐生物碱
• 英文名称: diethyl (4aS,5S,8S,13bR)-5-hydroxy-11,12-dimethoxy-6-oxospiro[1,2,4,5,8,9-hexahydroindolo[7a,1-a]isoquinoline-3,2'-1,3-dioxolane]-4a,8-dicarboxylate
• CAS: 157007-23-3
• 化学式: C₂₆H₃₃NO₁₀
• 分子量: 519.549
• InChiKey: AEIBYGWJIKTJRX-HEBBRHJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  130
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  diethyl (4aS,5S,8S,13bR)-5-hydroxy-11,12-dimethoxy-6-oxospiro[1,2,4,5,8,9-hexahydroindolo[7a,1-a]isoquinoline-3,2'-1,3-dioxolane]-4a,8-dicarboxylate 在 盐酸 作用下， 以95%的产率得到(5R,6S,7S,10S)-6,10-diethoxycarbonyl-7-hydroxy-15,16-dimethoxy-2,8-dioxoerythrinan
  参考文献：
  名称：

  Asymmetric (2+2) Photocycloaddition Reaction of a Chiral Dioxopyrroline to 2-(Trimethylsilyoxy)-butadiene: Chiral Synthesis of Erythrina Alkaloids.

  摘要：

  通过使用对映体纯的底物，阐明了异喹啉二氧代吡咯啉与 2-(rtimethylsilyloxy)丁二烯发生[2+2] 光环加成反应的详细立体化学途径。光加成物被转化为刺五加生物碱的合成中间体，提供了一种光学活性形式的高效合成方法。

  DOI：

  10.1248/cpb.42.1373
• 作为产物：
  描述：

  diethyl (4'aS,8'S,13'bR)-11',12'-dimethoxy-5',6'-dioxospiro[1,3-dioxolane-2,3'-2,4,8,9-tetrahydro-1H-indolo[7a,1-a]isoquinoline]-4'a,8'-dicarboxylate 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 以84%的产率得到diethyl (4aS,5S,8S,13bR)-5-hydroxy-11,12-dimethoxy-6-oxospiro[1,2,4,5,8,9-hexahydroindolo[7a,1-a]isoquinoline-3,2'-1,3-dioxolane]-4a,8-dicarboxylate
  参考文献：
  名称：

  Asymmetric (2+2) Photocycloaddition Reaction of a Chiral Dioxopyrroline to 2-(Trimethylsilyoxy)-butadiene: Chiral Synthesis of Erythrina Alkaloids.

  摘要：

  通过使用对映体纯的底物，阐明了异喹啉二氧代吡咯啉与 2-(rtimethylsilyloxy)丁二烯发生[2+2] 光环加成反应的详细立体化学途径。光加成物被转化为刺五加生物碱的合成中间体，提供了一种光学活性形式的高效合成方法。

  DOI：

  10.1248/cpb.42.1373

文献信息

• Chiral Synthesis of Erythrina Alkaloids. (2). Synthesis of enantio-Type Erythrinan Alkaloids Utilizing Asymmetric Acylation and Kinetic Resolution of Diastereomers.
  作者：Yoshisuke TSUDA、Shinzo HOSOI、Kazuya ISHIDA、Masako SANGAI

  DOI：10.1248/cpb.42.204

  日期：——

  Oxalylation of the enamino-ester 13 derived from the L-dopa derivative 12 gave the dioxopyrroline of (6S)-configuration (15A) diastereoselectively (50-60% diastereomer excess). This was converted to a mixture of erythrinans of (5S, 6R, 7R, 10S) and (5R, 6S, 7S, 10S) configuration by cyclization with BF3·Et2O. The de of the major diastereomer (A) was elevated to 82% by application of a kinetic resolution of diastereomers (partial hydrolysis of the ethylene acetal group), where the minor diastereomer (B) was hydrolyzed more rapidly. The acetal 17A which remained unchanged was converted, in several steps, to the enantio-type erythrinan alkaloid, (-)-3-demethoxyerythratidinone (-)-7, and also to the 1, 7-cycloerythrinan (-)-9, a key intermediate to Erythrina alkaloids. The more easily hydrolyzable diastereomer (B) was similarly converted to the enantiomer (+)-9. The mechanism of partial racemization, sometimes observed in the product, is discussed.

  由 L-多巴衍生物 12 衍生出的烯酰胺酯 13 通过草酰化反应，非对映选择性地得到了 (6S) 构型的二氧吡咯啉 (15A)（非对映异构体过量率为 50-60%）。通过与 BF3-Et2O 环化，将其转化为（5S, 6R, 7R, 10S）和（5R, 6S, 7S, 10S）构型的赤藓红混合物。通过非对映异构体的动力学解析（乙烯缩醛基团的部分水解），主要非对映异构体（A）的de 提高到 82%，而次要非对映异构体（B）的水解速度更快。保持不变的乙缩醛 17A 经过几个步骤转化为对映体型红花楠生物碱 (-)-3-demethoxyerythratidinone (-)-7，以及红花楠生物碱的关键中间体 1，7-环红花楠 (-)-9。更容易水解的非对映异构体（B）也同样转化为对映体（+）-9。本文讨论了有时在产品中观察到的部分消旋化机制。
• Synthesis of Erythrina and Related Alkaloids. Part XXXVII. Chiral synthesis of enantio-type erythrinan alkaloids utilizing asymmetric acylation and kinetic resolution of diastereomers.
  作者：Shinzo HOSOI、Kazuya ISHIDA、Masako SANGAI、Yoshisuke TSUDA

  DOI：10.1248/cpb.40.3115

  日期：——

  Chiral synthesis of an erythrinan alkaloid, (-)-3-demethoxyerythratidinone (11), as well as a versatile intermediate, the 1, 7-cycloerythrinan derivative (14) (both are of enantio-type) was achieved using asymmetric acylation and kinetic resolution starting from the L-dopa derivative (1).

  从 L-多巴衍生物 (1) 开始，通过不对称酰化和动力学解析，实现了一种赤藓楠生物碱--(-)-3-去甲氧基赤藓桔梗酮 (11) 和一种多功能中间体--1, 7-环赤藓楠衍生物 (14) 的手性合成（两者都是对映体类型）。
• Asymmetric (2+2) Photocycloaddition Reaction of a Chiral Dioxopyrroline to 2-(Trimethylsilyoxy)-butadiene: Chiral Synthesis of Erythrina Alkaloids.
  作者：Takehiro SANO、Makiko KAMIKO、Jun TODA、Shinzo HOSOI、Yoshisuke TSUDA

  DOI：10.1248/cpb.42.1373

  日期：——

  The detailed stereochemical pathway of [2+2] photocycloaddition reaction of isoquinolinodioxopyrroline to 2-(rtimethylsilyloxy)butadiene was clarified by using an enantiomerically pure substrate. The photoadducts were converted into the synthetic intermediates of Erythrina alkaloids, providing an efficient synthetic method in optically active forms.

  通过使用对映体纯的底物，阐明了异喹啉二氧代吡咯啉与 2-(rtimethylsilyloxy)丁二烯发生[2+2] 光环加成反应的详细立体化学途径。光加成物被转化为刺五加生物碱的合成中间体，提供了一种光学活性形式的高效合成方法。