methyl (1R,10R,12S,18S,20S)-10-chloro-12-ethyl-18-hydroxy-17-oxa-8,16-diazapentacyclo[10.7.1.01,9.02,7.016,20]icosa-2,4,6,8-tetraene-10-carboxylate | 163814-09-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉类
• 英文名称: methyl (1R,10R,12S,18S,20S)-10-chloro-12-ethyl-18-hydroxy-17-oxa-8,16-diazapentacyclo[10.7.1.01,9.02,7.016,20]icosa-2,4,6,8-tetraene-10-carboxylate
• CAS: 163814-09-3
• 化学式: C₂₁H₂₅ClN₂O₄
• 分子量: 404.894
• InChiKey: PCFULGMPFKZJQI-MFZGXCKPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  71.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (1R,10R,12S,18S,20S)-10-chloro-12-ethyl-18-hydroxy-17-oxa-8,16-diazapentacyclo[10.7.1.01,9.02,7.016,20]icosa-2,4,6,8-tetraene-10-carboxylate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以52%的产率得到methyl (4aS,12aS)-4a-ethyl-1-hydroxy-7-(2-oxoethyl)-2,3,4,12a-tetrahydroindolo[1,2-a][1,8]naphthyridine-6-carboxylate
  参考文献：
  名称：

  New Rearrangement of an Aspidosperma Alkaloid. The First Biomimetic Entry in the Goniomitine Skeleton

  摘要：

  The first biomimetic approach to the skeleton of goniomitine (12) from an Aspidosperma alkaloid is described. With 16-chloro-1-dehydro-5-methoxyvincadifforme (4) (easily available from vincadifformine (1) as starting material, the rearrangement is performed in two steps: (a) Oxidation of 4 by m-CPBA followed by methanolysis affords the hemiketal 10 with a tetrahydro-1,2-oxazine structure for ring C, and (b) acid-catalyzed reaction on 10 provides either a mixture of both rearranged compounds 15 and 16 or 15 alone according to reaction time. Mechanisms of formation of 10, 15, and 16 are discussed.

  DOI：

  10.1021/jo00116a009
• 作为产物：
  描述：

  methyl (1R,10R,12S,20S)-10-chloro-18-(3-chlorobenzoyl)oxy-12-ethyl-17-oxa-8,16-diazapentacyclo[10.7.1.01,9.02,7.016,20]icosa-2,4,6,8-tetraene-10-carboxylate 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 0.08h， 以71%的产率得到methyl (1R,10R,12S,18S,20S)-10-chloro-12-ethyl-18-hydroxy-17-oxa-8,16-diazapentacyclo[10.7.1.01,9.02,7.016,20]icosa-2,4,6,8-tetraene-10-carboxylate
  参考文献：
  名称：

  New Rearrangement of an Aspidosperma Alkaloid. The First Biomimetic Entry in the Goniomitine Skeleton

  摘要：

  The first biomimetic approach to the skeleton of goniomitine (12) from an Aspidosperma alkaloid is described. With 16-chloro-1-dehydro-5-methoxyvincadifforme (4) (easily available from vincadifformine (1) as starting material, the rearrangement is performed in two steps: (a) Oxidation of 4 by m-CPBA followed by methanolysis affords the hemiketal 10 with a tetrahydro-1,2-oxazine structure for ring C, and (b) acid-catalyzed reaction on 10 provides either a mixture of both rearranged compounds 15 and 16 or 15 alone according to reaction time. Mechanisms of formation of 10, 15, and 16 are discussed.

  DOI：

  10.1021/jo00116a009

文献信息

• New Rearrangement of an Aspidosperma Alkaloid. The First Biomimetic Entry in the Goniomitine Skeleton
  作者：Guy Lewin、Corinne Schaeffer、Pierre Herve Lambert

  DOI：10.1021/jo00116a009

  日期：1995.6

  The first biomimetic approach to the skeleton of goniomitine (12) from an Aspidosperma alkaloid is described. With 16-chloro-1-dehydro-5-methoxyvincadifforme (4) (easily available from vincadifformine (1) as starting material, the rearrangement is performed in two steps: (a) Oxidation of 4 by m-CPBA followed by methanolysis affords the hemiketal 10 with a tetrahydro-1,2-oxazine structure for ring C, and (b) acid-catalyzed reaction on 10 provides either a mixture of both rearranged compounds 15 and 16 or 15 alone according to reaction time. Mechanisms of formation of 10, 15, and 16 are discussed.