(S)-1-benzo[1,3]dioxol-5-yl-2-benzyl-2,3,4,9-tetrahydro-1H-β-carboline-(R)-3-carboxylic acid methyl ester | 497182-99-7

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 哈马拉生物碱
• 英文名称: (S)-1-benzo[1,3]dioxol-5-yl-2-benzyl-2,3,4,9-tetrahydro-1H-β-carboline-(R)-3-carboxylic acid methyl ester
• 英文别名: (1S,3R)-methyl 1-(benzo[d][1,3]dioxol-5-yl)-2-benzyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylate；methyl (1S,3R)-1-(1,3-benzodioxol-5-yl)-2-benzyl-1,3,4,9-tetrahydropyrido[3,4-b]indole-3-carboxylate
• CAS: 497182-99-7
• 化学式: C₂₇H₂₄N₂O₄
• 分子量: 440.499
• InChiKey: CPMRCYQWJGICSD-GJZUVCINSA-N

物化性质

• 沸点：
  585.5±50.0 °C(Predicted)
• 密度：
  1.330±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  33
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  63.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-1-benzo[1,3]dioxol-5-yl-2-benzyl-2,3,4,9-tetrahydro-1H-β-carboline-(R)-3-carboxylic acid methyl ester 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙腈 为溶剂， 60.0 ℃ 、111.46 kPa 条件下， 反应 8.0h， 以95%的产率得到(1S,3R)-甲基-1,2,3,4-四氢-1-(3,4-亚甲二氧基苯基)-9H-吡啶并[3,4-b]吲哚-3-羧酸酯
  参考文献：
  名称：

  Highly stereoselective transformation of (1S,3S)-cis-1,3-disubstituted tetrahydro-β-carbolines into (1S,3R)-trans-1,3-disubstituted tetrahydro-β-carbolines: an improved asymmetric synthesis of tadalafil from l-tryptophan

  摘要：

  An efficient and general method for the highly stereoselective transformation of (1S,3S)-cis-1,3-disubstituted 1,2,3,4-tetrahydro-beta-carbolines (THBCs) into (15,3R)-trans-1,3-disubstituted THBCs is described. The method contains the following three steps: the enantiomerically pure (1S,3S)-cis-1,3-disubstituted THBCs 1 were first converted into (1S,3S)-cis-1,2,3-trisubstituted THBCs 2 by N-1-naphthylmethylation/benzylation; (15,3S)-cis-1,2,3-trisubstituted THBCs 2 were then converted into (1S,3R)-trans-1,2,3-trisubstituted THBCs 3 in high yields and with high stereoselectivities via a base-catalyzed epimerization at C-3; (1S,3R)-trans-1,2,3-trisubstituted THBCs 3 were subsequently converted into (15,3R)-trans-1,3-disubstituted THBCs 4 after reductive removal of the 1-naphthylmethyl/benzyl group. In addition, as an application of this method, an improved and highly stereoselective synthesis of the PDE5 inhibitor tadalafil (Cialis (R)) starting from natural and less expensive L-tryptophan was developed. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.06.006
• 作为产物：
  描述：

  D-色氨酸甲酯 在 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.0h， 生成 (S)-1-benzo[1,3]dioxol-5-yl-2-benzyl-2,3,4,9-tetrahydro-1H-β-carboline-(R)-3-carboxylic acid methyl ester
  参考文献：
  名称：

  过氧化钾可作为温特费尔德氧化β-咔啉的替代试剂。

  摘要：

  研究了过氧化钾作为温特费尔特反应的替代氧化剂。发现KO（2）优于原始的Winterfeldt协议用于碱敏底物。[反应-见文字]

  DOI：

  10.1021/ol0271279

文献信息

• Potassium Superoxide as an Alternative Reagent for Winterfeldt Oxidation of β-Carbolines
  作者：Weiqin Jiang、Xuqing Zhang、Zhihua Sui

  DOI：10.1021/ol0271279

  日期：2003.1.1

  Potassium superoxide was examined as an alternative oxidation reagent for the Winterfeldt reaction. KO(2) was found to be superior to the original Winterfeldt protocol for base-sensitive substrates. [reaction--see text]

  研究了过氧化钾作为温特费尔特反应的替代氧化剂。发现KO（2）优于原始的Winterfeldt协议用于碱敏底物。[反应-见文字]
• Highly stereoselective transformation of (1S,3S)-cis-1,3-disubstituted tetrahydro-β-carbolines into (1S,3R)-trans-1,3-disubstituted tetrahydro-β-carbolines: an improved asymmetric synthesis of tadalafil from l-tryptophan
  作者：Jing Dong、Tian-Zhuo Meng、Xiao-Xin Shi、Wen-Hui Zou、Xia Lu

  DOI：10.1016/j.tetasy.2013.06.006

  日期：2013.8

  An efficient and general method for the highly stereoselective transformation of (1S,3S)-cis-1,3-disubstituted 1,2,3,4-tetrahydro-beta-carbolines (THBCs) into (15,3R)-trans-1,3-disubstituted THBCs is described. The method contains the following three steps: the enantiomerically pure (1S,3S)-cis-1,3-disubstituted THBCs 1 were first converted into (1S,3S)-cis-1,2,3-trisubstituted THBCs 2 by N-1-naphthylmethylation/benzylation; (15,3S)-cis-1,2,3-trisubstituted THBCs 2 were then converted into (1S,3R)-trans-1,2,3-trisubstituted THBCs 3 in high yields and with high stereoselectivities via a base-catalyzed epimerization at C-3; (1S,3R)-trans-1,2,3-trisubstituted THBCs 3 were subsequently converted into (15,3R)-trans-1,3-disubstituted THBCs 4 after reductive removal of the 1-naphthylmethyl/benzyl group. In addition, as an application of this method, an improved and highly stereoselective synthesis of the PDE5 inhibitor tadalafil (Cialis (R)) starting from natural and less expensive L-tryptophan was developed. (C) 2013 Elsevier Ltd. All rights reserved.