methyl 4-bromo-α-2-propenyl-DL-tryptophan | 160798-15-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 4-bromo-α-2-propenyl-DL-tryptophan
• CAS: 160798-15-2
• 化学式: C₁₅H₁₇BrN₂O₂
• 分子量: 337.216
• InChiKey: MPPVAXZYWCJGNH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  68.11
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl 4-bromo-α-2-propenyl-DL-tryptophan 在 palladium on activated charcoal 、 palladium diacetate 吡啶 、 氢气 、 三乙胺 、 三(邻甲基苯基)磷 作用下， 以 四氢呋喃 为溶剂， 反应 42.0h， 生成 cis/trans methyl 8-amino-6-methyl-6,7,8,9-tetrahydro-2H-2-azabenzoazulene-8-carboxylate
  参考文献：
  名称：

  Synthesis of Conformationally Constrained Tryptophan Derivatives

  摘要：

  Methyl 1,3,4,5-tetrahydro-4-[[(phenylmethoxy)carbonyl]amino]-1H-cyclooct[cd]indole-4-carboxylate, methyl 3,4,5,6-tetrahydro-6-methylene-4-[[(phenylmethoxy)carbonyl]amino]-1H-cyclohept[cd]indole-4-carboxylate, and methyl 3,4-dihydro-6-methyl-4-[[(phenylmethoxy)carbonyl]amino]-1H-cyclohept-[cd]indole-4-carboxylate are three novel 3,4-fused tryptophan analogues which have been designed and synthesized for use in peptide/peptoid conformation elucidation studies. These derivatives have a ring that bridges the alpha-carbon and the 4-position of the indole ring, thus limiting the conformational flexibility of the side chain while leaving both amine and carboxylic acid groups free for further derivatization. The synthesis proceeded from 4-bromoindole via methyl 3-(4-bromo-1H-indol-3-yl)-2-(formylamino)-2-propenoate in which the carbon-carbon double bond was selectively reduced in the presence of the aromatic halide and then converted into methyl 4-bromo-N-[(phenylmethoxy)carbonyl]-alpha-2-propenyl-DL-tryptophan. Palladium-catalyzed cyclization of this alpha-propenyl tryptophan derivative proceeded smoothly under Heck conditions to give the compounds described above, yielding both the seven- and eight-membered constrained ring analogues. Functionalization of these key materials has been demonstrated.

  DOI：

  10.1021/jo00095a015
• 作为产物：
  描述：

  methyl 3-(4-bromo-1H-indol-3-yl)-2-(formylamino)-2-propenoate 在 Wilkinson's catalyst 盐酸 、 4-二甲氨基吡啶 、 三光气 、 氢气 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， -78.0~25.0 ℃ 、448.16 kPa 条件下， 反应 97.5h， 生成 methyl 4-bromo-α-2-propenyl-DL-tryptophan
  参考文献：
  名称：

  Synthesis of Conformationally Constrained Tryptophan Derivatives

  摘要：

  Methyl 1,3,4,5-tetrahydro-4-[[(phenylmethoxy)carbonyl]amino]-1H-cyclooct[cd]indole-4-carboxylate, methyl 3,4,5,6-tetrahydro-6-methylene-4-[[(phenylmethoxy)carbonyl]amino]-1H-cyclohept[cd]indole-4-carboxylate, and methyl 3,4-dihydro-6-methyl-4-[[(phenylmethoxy)carbonyl]amino]-1H-cyclohept-[cd]indole-4-carboxylate are three novel 3,4-fused tryptophan analogues which have been designed and synthesized for use in peptide/peptoid conformation elucidation studies. These derivatives have a ring that bridges the alpha-carbon and the 4-position of the indole ring, thus limiting the conformational flexibility of the side chain while leaving both amine and carboxylic acid groups free for further derivatization. The synthesis proceeded from 4-bromoindole via methyl 3-(4-bromo-1H-indol-3-yl)-2-(formylamino)-2-propenoate in which the carbon-carbon double bond was selectively reduced in the presence of the aromatic halide and then converted into methyl 4-bromo-N-[(phenylmethoxy)carbonyl]-alpha-2-propenyl-DL-tryptophan. Palladium-catalyzed cyclization of this alpha-propenyl tryptophan derivative proceeded smoothly under Heck conditions to give the compounds described above, yielding both the seven- and eight-membered constrained ring analogues. Functionalization of these key materials has been demonstrated.

  DOI：

  10.1021/jo00095a015

文献信息

• Conformationally constrained amino acids: Synthesis of novel 3,4-cyclised tryptophans
  作者：David C. Horwell、Paul D. Nichols、Edward Roberts

  DOI：10.1016/s0040-4039(00)76005-9

  日期：1994.1

  The synthesis of novel conformationally constrained tryptophan derivatives via a Heck-type cyclisation of an unusual α-substituted amino acid is described.

  描述了通过不寻常的α-取代的氨基酸的Heck型环化合成新的构象受限的色氨酸衍生物。