(1R^*,5R^*,6S^*)-6-carbomethoxy-4,6-dimethoxybicyclo<3.1.0>hex-3-en-2-one | 136315-15-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R^*,5R^*,6S^*)-6-carbomethoxy-4,6-dimethoxybicyclo<3.1.0>hex-3-en-2-one
• 英文别名: methyl (1R,5R,6R)-2,6-dimethoxy-4-oxobicyclo[3.1.0]hex-2-ene-6-carboxylate
• CAS: 136315-15-6
• 化学式: C₁₀H₁₂O₅
• 分子量: 212.202
• InChiKey: ACXSHJMNFZVCFD-WEDXCCLWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (1R^*,5R^*,6R^*)-6-carbomethoxy-4,6-dimethoxybicyclo<3.1.0>hex-3-en-2-one 以 苯 为溶剂， 反应 3.0h， 以6%的产率得到4-羟基-2,6-二甲氧基苯甲酸甲酯
  参考文献：
  名称：

  Substituent effects on the photorearrangements of 4-alkoxy-4-carbomethoxy-3-methoxy-2,5-cyclohexadien-1-ones

  摘要：

  Enantiomerically enriched 4-carbomethoxy-3,4-dimethoxy-2,5-cyclohexadien-1-one (1) undergoes a completely diastereoselective (but not enantiospecific) type A photorearrangement at 366 nm to give 6-carbomethoxy-4,6-dimethoxybicyclo[3.1.0(1,5)]hex-3-en-2-one (2) in 81% isolated yield. A chiral NMR shift study indicates that 1 undergoes partial loss of absolute configuration at C(4) during irradiation. Bicyclohexenone 2 is photostable at 366 nm but rearranges to its diastereoisomer 3 and phenols 4 and 5 at > 300 nm. It is proposed that ground-state conformational effects control the type A photoreactivity of 1 and that rearrangement to 2 occurs in accord with the principle of least motion in the transition states for rearrangements to diastereomerically related zwitterions 1a and 1b (Scheme III). The intramolecular 2 + 2 photocycloaddition of 4-carbomethoxy-3-methoxy-4-(1'-oxa-3'-butenyl)-2,5-cyclohexadien-1-one (9) gives a mixture of 7-oxatricyclodecenones 10 (58%) and 11 (18%), without interference from type A photoreactivity.

  DOI：

  10.1021/jo00022a033