N-Carbomethoxyhydrastinin | 35287-58-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: N-Carbomethoxyhydrastinin
• 英文别名: [2-(6-formyl-benzo[1,3]dioxol-5-yl)-ethyl]-methyl-carbamic acid methyl ester；methyl N-[2-(6-formyl-1,3-benzodioxol-5-yl)ethyl]-N-methylcarbamate
• CAS: 35287-58-2
• 化学式: C₁₃H₁₅NO₅
• 分子量: 265.266
• InChiKey: RICZYFZQDJJAQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-Carbomethoxyhydrastinin 在 盐酸 、 lithium aluminium tetrahydride 、 硫酸 、 2,2,6,6-tetramethylpiperidinyl-lithium 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 氯仿 为溶剂， 反应 10.5h， 生成 Peshawarin
  参考文献：
  名称：

  Reaction of Benzocyclobutene Oxides with Aldehydes: Synthesis of Peshawarine and Other 3,4-Dihydroisocoumarins

  摘要：

  Deprotonation of benzocyclobutenols 6 in the presence of aromatic aldehydes affords benzopyranols 7 in high yield. In the key step of this process, an o-tolualdehyde anion generated by the known ring-opening of benzocyclobutenoxides adds to the aldehyde to give 7 which is easily oxidized to 3-substituted 3,4-dihydroisocoumarins 8 including intermediates in some natural product syntheses. For example, reaction of 6-methoxybenzocyclobutenol (1) with LTMP and p-anisaldehyde gave in 96% yield the benzopyranol 16, which subsequently was converted to (+/-)-hydrangenol (17). Similar treatment of 1 with LDA and isovanillin benzyl ether afforded the benzopyranol 19 (87% yield) which already has been converted to (+/-)-phyllodulcin (21). Finally, reaction of 5,6-(methylenedioxy)-benzocyclobutenol (10) with LTMP and the aldehyde 26 (from treatment of hydrastinine with ClCO2-Me) followed by methanolysis produced the acetal 28 in 96% yield. The overall yield was 65% for the five-step synthesis of the alkaloid (+/-)-peshawawine (24) from 10 and 26. Extension of the process to aliphatic aldehydes was illustrated by the preparation of 32 from benzocyclobutenol and isobutyraldehyde in 69% overall yield after oxidation with PCC.

  DOI：

  10.1021/jo00094a022

文献信息

• Reaction of Benzocyclobutene Oxides with Aldehydes: Synthesis of Peshawarine and Other 3,4-Dihydroisocoumarins
  作者：John J. Fitzgerald、Alex R. Pagano、Vianne M. Sakoda、R. A. Olofson

  DOI：10.1021/jo00094a022

  日期：1994.7

  Deprotonation of benzocyclobutenols 6 in the presence of aromatic aldehydes affords benzopyranols 7 in high yield. In the key step of this process, an o-tolualdehyde anion generated by the known ring-opening of benzocyclobutenoxides adds to the aldehyde to give 7 which is easily oxidized to 3-substituted 3,4-dihydroisocoumarins 8 including intermediates in some natural product syntheses. For example, reaction of 6-methoxybenzocyclobutenol (1) with LTMP and p-anisaldehyde gave in 96% yield the benzopyranol 16, which subsequently was converted to (+/-)-hydrangenol (17). Similar treatment of 1 with LDA and isovanillin benzyl ether afforded the benzopyranol 19 (87% yield) which already has been converted to (+/-)-phyllodulcin (21). Finally, reaction of 5,6-(methylenedioxy)-benzocyclobutenol (10) with LTMP and the aldehyde 26 (from treatment of hydrastinine with ClCO2-Me) followed by methanolysis produced the acetal 28 in 96% yield. The overall yield was 65% for the five-step synthesis of the alkaloid (+/-)-peshawawine (24) from 10 and 26. Extension of the process to aliphatic aldehydes was illustrated by the preparation of 32 from benzocyclobutenol and isobutyraldehyde in 69% overall yield after oxidation with PCC.