4,18-Dihydroxy-11,25-bis-hydroxymethyl-3,17-dimethyl-1,15-diaza-cyclooctacosane-1,15-dicarboxylic acid di-tert-butyl ester | 158835-79-1

• 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: 4,18-Dihydroxy-11,25-bis-hydroxymethyl-3,17-dimethyl-1,15-diaza-cyclooctacosane-1,15-dicarboxylic acid di-tert-butyl ester
• 英文别名: Ditert-butyl 4,18-dihydroxy-11,25-bis(hydroxymethyl)-3,17-dimethyl-1,15-diazacyclooctacosane-1,15-dicarboxylate
• CAS: 158835-79-1
• 化学式: C₄₀H₇₈N₂O₈
• 分子量: 715.068
• InChiKey: XYVMIQJFXOESDC-UHFFFAOYSA-N

物化性质

• 沸点：
  784.9±45.0 °C(predicted)
• 密度：
  0.987±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  50
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  140
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4,18-Dihydroxy-11,25-bis-hydroxymethyl-3,17-dimethyl-1,15-diaza-cyclooctacosane-1,15-dicarboxylic acid di-tert-butyl ester 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Total Synthesis of Petrosin, Petrosin A, and Petrosin B

  摘要：

  The petrosins are a family of marine alkaloids that includes the chiral, racemic isomer petrosin (1), the meso isomer petrosin A (2), and the chiral, scalemic isomer petrosin B (3). Monte Carlo molecular mechanics calculations indicated that petrosin (1) is the most stable isomer of the group, suggesting that it might be synthesized by a route that utilizes thermodynamic control for establishing the relative configurations of the eight stereocenters. The model synthesis summarized in Scheme 1 showed that intramolecular Mannich condensation is a viable route to the quinolizidone subunit of the petrosins and that this synthesis gives isomer 5, having the relative configuration found in petrosin and petrosin A, as the kinetic product. Equilibration studies with this isomer afforded an approximate equimolar mixture of 5 and diastereomer 6, having the relative configuration found in one of the two quinolizidone milts of petrosin B. On the basis of this model study, a "stereo-uncontrolled" synthesis of petrosin was carried out, as summarized in Schemes 3-5. The key step of this synthesis is a "double-barrelled" intramolecular Mannich condensation of a diamino keto dialdehyde. This transformation provides crystalline petrosin in 23% yield, along with about 37% of a mixture of petrosin diastereomers. Although simple acid- and Lewis acid-mediated equilibrations of this mixture of diastereomers were not successful, the derived mixture of bis-butylimines undergoes equilibration upon treatment with protic acid to give a mixture that is greatly enriched in petrosin, relative to the other isomers. Crystallization of this equilibration mixture provided another 10% of petrosin, bringing the overall yield of petrosin to 33%. In the course of the equilibration studies, pure samples of petrosin A (2), petrosin B (3), and petrosin B' (7) were isolated and characterized.

  DOI：

  10.1021/jo9801768
• 作为产物：
  描述：

  10-Cyano-8-formyl-decanoic acid methyl ester 在 platinum(IV) oxide 吡啶 、 咪唑 、 盐酸 、 sodium hydroxide 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 正丁基锂 、 氢气 、 二异丁基氢化铝 、 碳酸氢钠 、 1-羟基苯并三唑 、 溶剂黄146 、 二异丙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， -93.0~90.0 ℃ 、365.42 kPa 条件下， 反应 149.58h， 生成 4,18-Dihydroxy-11,25-bis-hydroxymethyl-3,17-dimethyl-1,15-diaza-cyclooctacosane-1,15-dicarboxylic acid di-tert-butyl ester
  参考文献：
  名称：

  Total Synthesis of Petrosin, Petrosin A, and Petrosin B

  摘要：

  The petrosins are a family of marine alkaloids that includes the chiral, racemic isomer petrosin (1), the meso isomer petrosin A (2), and the chiral, scalemic isomer petrosin B (3). Monte Carlo molecular mechanics calculations indicated that petrosin (1) is the most stable isomer of the group, suggesting that it might be synthesized by a route that utilizes thermodynamic control for establishing the relative configurations of the eight stereocenters. The model synthesis summarized in Scheme 1 showed that intramolecular Mannich condensation is a viable route to the quinolizidone subunit of the petrosins and that this synthesis gives isomer 5, having the relative configuration found in petrosin and petrosin A, as the kinetic product. Equilibration studies with this isomer afforded an approximate equimolar mixture of 5 and diastereomer 6, having the relative configuration found in one of the two quinolizidone milts of petrosin B. On the basis of this model study, a "stereo-uncontrolled" synthesis of petrosin was carried out, as summarized in Schemes 3-5. The key step of this synthesis is a "double-barrelled" intramolecular Mannich condensation of a diamino keto dialdehyde. This transformation provides crystalline petrosin in 23% yield, along with about 37% of a mixture of petrosin diastereomers. Although simple acid- and Lewis acid-mediated equilibrations of this mixture of diastereomers were not successful, the derived mixture of bis-butylimines undergoes equilibration upon treatment with protic acid to give a mixture that is greatly enriched in petrosin, relative to the other isomers. Crystallization of this equilibration mixture provided another 10% of petrosin, bringing the overall yield of petrosin to 33%. In the course of the equilibration studies, pure samples of petrosin A (2), petrosin B (3), and petrosin B' (7) were isolated and characterized.

  DOI：

  10.1021/jo9801768

文献信息

• Total Synthesis of Petrosin
  作者：Robert W. Scott、James R. Epperson、Clayton H. Heathcock

  DOI：10.1021/ja00098a073

  日期：1994.9
• Total Synthesis of Petrosin, Petrosin A, and Petrosin B
  作者：Robert W. Scott、James Epperson、Clayton H. Heathcock

  DOI：10.1021/jo9801768

  日期：1998.7.1

  The petrosins are a family of marine alkaloids that includes the chiral, racemic isomer petrosin (1), the meso isomer petrosin A (2), and the chiral, scalemic isomer petrosin B (3). Monte Carlo molecular mechanics calculations indicated that petrosin (1) is the most stable isomer of the group, suggesting that it might be synthesized by a route that utilizes thermodynamic control for establishing the relative configurations of the eight stereocenters. The model synthesis summarized in Scheme 1 showed that intramolecular Mannich condensation is a viable route to the quinolizidone subunit of the petrosins and that this synthesis gives isomer 5, having the relative configuration found in petrosin and petrosin A, as the kinetic product. Equilibration studies with this isomer afforded an approximate equimolar mixture of 5 and diastereomer 6, having the relative configuration found in one of the two quinolizidone milts of petrosin B. On the basis of this model study, a "stereo-uncontrolled" synthesis of petrosin was carried out, as summarized in Schemes 3-5. The key step of this synthesis is a "double-barrelled" intramolecular Mannich condensation of a diamino keto dialdehyde. This transformation provides crystalline petrosin in 23% yield, along with about 37% of a mixture of petrosin diastereomers. Although simple acid- and Lewis acid-mediated equilibrations of this mixture of diastereomers were not successful, the derived mixture of bis-butylimines undergoes equilibration upon treatment with protic acid to give a mixture that is greatly enriched in petrosin, relative to the other isomers. Crystallization of this equilibration mixture provided another 10% of petrosin, bringing the overall yield of petrosin to 33%. In the course of the equilibration studies, pure samples of petrosin A (2), petrosin B (3), and petrosin B' (7) were isolated and characterized.