(-)-methyl (2S,3aS,5R,11bR)-2-(methoxycarbonyl)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate | 219557-89-8

• 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: (-)-methyl (2S,3aS,5R,11bR)-2-(methoxycarbonyl)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
• 英文别名: dimethyl (2S,3aS,5S,11bR)-3-benzyl-5-[(E)-prop-1-enyl]-1,2,3a,4,5,7-hexahydropyrrolo[2,3-d]carbazole-2,6-dicarboxylate
• CAS: 219557-89-8
• 化学式: C₂₈H₃₀N₂O₄
• 分子量: 458.557
• InChiKey: UESHAWYNYQAZPB-HXAHZZCQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  67.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (-)-methyl (2S,3aS,5R,11bR)-2-(methoxycarbonyl)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate 在 potassium osmate(VI) 、 钾硼氢 、 potassium metaperiodate 、 氨 、 N,N-二异丙基乙胺 、 三氟乙酸酐 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 130.67h， 生成 (+/-)-methyl (2S*,3aS*,5R*,11bR*)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
  参考文献：
  名称：

  Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 10. An Enantioselective Synthesis of (−)-Strychnine through the Wieland−Gumlich Aldehyde

  摘要：

  Condensations of L-tryptophan-derived 2-[(methoxycarbonyl)methyl]-3-[2(S)-(benzyloxycarbonyl)- 2-(N-b-benzylamino)ethyl]indole (6) with 4,4-dimethoxyacrolein or with 2,4-hexadienal, followed by removal of the tryptophanyl ester function, respectively gave the tetracyclic acetal (-)-methyl (2S, 3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(dimethoxymethyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (10) or the tetracyclic olefin (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (14). Their respective hydrolysis or oxidation provided, enantioselectively, the tetracyclic aldehyde (-)-methyl (2S,3aS,5R,11bR)3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (5). Its reaction with tri-n-butyl-1-(ethoxy)ethoxymethyltin and n-butyllithium, followed by oxidation of the resultant alcohol (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1 xi-hydroxy-2-((1-ethoxy-ethoxy))ethyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (16) and cyclization furnished the pentacyclic ketone (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-3,5-ethano-12-oxo-1H-pyrrolo-2,3-d]carbazole-6-carboxylate (15). A Horner-Emmons condensation led to the unsaturated esters (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahodro-3,5-ethano-12-(E and Z)-[(methoxycarbonyl)-methylene]-1H-pyrrolo[2,3-d]carbazole-6-carboxylates(19 and 20) with 17:1 E/Z selectivity. Reductions of the ester and vinylogous urethane functions in 19 led to the Wieland-Gumlich aldehyde 3 as a 6:1 anomeric hemiacetal mixture. Its condensation with malonic acid provided (-)-strychnine (1) in 5.3% overall yield and 14 steps from the tryptophan derivative 6.

  DOI：

  10.1021/jo9813989
• 作为产物：
  描述：

  methyl N-benzyl-L-tryptophanate 在 三氟甲磺酸三甲基硅酯 、 水 、 三乙胺 、 对苯二酚 、 苯甲酸 、 lithium chloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 17.0h， 生成 (-)-methyl (2S,3aS,5R,11bR)-2-(methoxycarbonyl)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
  参考文献：
  名称：

  Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 10. An Enantioselective Synthesis of (−)-Strychnine through the Wieland−Gumlich Aldehyde

  摘要：

  Condensations of L-tryptophan-derived 2-[(methoxycarbonyl)methyl]-3-[2(S)-(benzyloxycarbonyl)- 2-(N-b-benzylamino)ethyl]indole (6) with 4,4-dimethoxyacrolein or with 2,4-hexadienal, followed by removal of the tryptophanyl ester function, respectively gave the tetracyclic acetal (-)-methyl (2S, 3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(dimethoxymethyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (10) or the tetracyclic olefin (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (14). Their respective hydrolysis or oxidation provided, enantioselectively, the tetracyclic aldehyde (-)-methyl (2S,3aS,5R,11bR)3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (5). Its reaction with tri-n-butyl-1-(ethoxy)ethoxymethyltin and n-butyllithium, followed by oxidation of the resultant alcohol (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1 xi-hydroxy-2-((1-ethoxy-ethoxy))ethyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (16) and cyclization furnished the pentacyclic ketone (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-3,5-ethano-12-oxo-1H-pyrrolo-2,3-d]carbazole-6-carboxylate (15). A Horner-Emmons condensation led to the unsaturated esters (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahodro-3,5-ethano-12-(E and Z)-[(methoxycarbonyl)-methylene]-1H-pyrrolo[2,3-d]carbazole-6-carboxylates(19 and 20) with 17:1 E/Z selectivity. Reductions of the ester and vinylogous urethane functions in 19 led to the Wieland-Gumlich aldehyde 3 as a 6:1 anomeric hemiacetal mixture. Its condensation with malonic acid provided (-)-strychnine (1) in 5.3% overall yield and 14 steps from the tryptophan derivative 6.

  DOI：

  10.1021/jo9813989

文献信息

• Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 10. An Enantioselective Synthesis of (−)-Strychnine through the Wieland−Gumlich Aldehyde
  作者：Martin E. Kuehne、Feng Xu

  DOI：10.1021/jo9813989

  日期：1998.12.1

  Condensations of L-tryptophan-derived 2-[(methoxycarbonyl)methyl]-3-[2(S)-(benzyloxycarbonyl)- 2-(N-b-benzylamino)ethyl]indole (6) with 4,4-dimethoxyacrolein or with 2,4-hexadienal, followed by removal of the tryptophanyl ester function, respectively gave the tetracyclic acetal (-)-methyl (2S, 3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(dimethoxymethyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (10) or the tetracyclic olefin (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (14). Their respective hydrolysis or oxidation provided, enantioselectively, the tetracyclic aldehyde (-)-methyl (2S,3aS,5R,11bR)3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (5). Its reaction with tri-n-butyl-1-(ethoxy)ethoxymethyltin and n-butyllithium, followed by oxidation of the resultant alcohol (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1 xi-hydroxy-2-((1-ethoxy-ethoxy))ethyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (16) and cyclization furnished the pentacyclic ketone (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-3,5-ethano-12-oxo-1H-pyrrolo-2,3-d]carbazole-6-carboxylate (15). A Horner-Emmons condensation led to the unsaturated esters (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahodro-3,5-ethano-12-(E and Z)-[(methoxycarbonyl)-methylene]-1H-pyrrolo[2,3-d]carbazole-6-carboxylates(19 and 20) with 17:1 E/Z selectivity. Reductions of the ester and vinylogous urethane functions in 19 led to the Wieland-Gumlich aldehyde 3 as a 6:1 anomeric hemiacetal mixture. Its condensation with malonic acid provided (-)-strychnine (1) in 5.3% overall yield and 14 steps from the tryptophan derivative 6.