(+)-2-(ethenyloxy)-3,7,7-trimethylbicyclo[4.1.0]heptane | 339307-77-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+)-2-(ethenyloxy)-3,7,7-trimethylbicyclo[4.1.0]heptane
• 英文别名: (+)-2-isocaranyl vinyl ether；(1S,2R,3S,6R)-2-ethenoxy-3,7,7-trimethylbicyclo[4.1.0]heptane
• CAS: 339307-77-6
• 化学式: C₁₂H₂₀O
• 分子量: 180.29
• InChiKey: NQIPWALXSIRELR-LNFKQOIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-Butenoic acid, 3-[(1E)-(aminocarbonyl)azo]-, ethyl ester, (2E)- 、 (+)-2-(ethenyloxy)-3,7,7-trimethylbicyclo[4.1.0]heptane 以 水 为溶剂， 反应 68.0h， 生成 ethyl (4S,6R)-cis-1-carbamoyl-6-(3,7,7-trimethylbicyclo[4.1.0]hept-2-yloxy)-1,4,5,6-tetrahydro-3-methylpyridazine-4-carboxylate 、 ethyl (4R,6R)-trans-1-carbamoyl-6-(3,7,7-trimethylbicyclo[4.1.0]hept-2-yloxy)-1,4,5,6-tetrahydro-3-methylpyridazine-4-carboxylate 、 ethyl (4S,6S)-trans-1-carbamoyl-6-(3,7,7-trimethylbicyclo[4.1.0]hept-2-yloxy)-1,4,5,6-tetrahydro-3-methylpyridazine-4-carboxylate 、 ethyl (4R,6S)-cis-1-carbamoyl-6-(3,7,7-trimethylbicyclo[4.1.0]hept-2-yloxy)-1,4,5,6-tetrahydro-3-methylpyridazine-4-carboxylate
  参考文献：
  名称：

  `Inverse-Electron-Demand'Diels-Alder Reactions of (E)-3-Diazenylbut-2-enes in Water

  摘要：

  The cycloadditions of (E)-3-diazenylbul-2-enes 1 with a variety of alkenes 2-6 were carried out in water as well as in organic solvents. The reactions were always faster in heterogeneous aqueous medium than in the organic solvents. These conjugated diazenyl-alkenes behave mainly as heterodienes. and the Diels-Alder adducts are the sole or at least main reaction products. Pyrroles derived from zwitterionic [3 + 2] cycloaddition reactions were observed in some cases. The cycloaddition of 1a with (+)-2-(ethenyloxy)-3,7,7-trimethylbicycloclo[4.1.0]heptane (5) is the first example of an asymmetric 'inverse electron-demand' Diels-Alder reaction carried out in pure water.

  DOI：

  10.1002/1522-2675(20010228)84:2<513::aid-hlca513>3.0.co;2-s
• 作为产物：
  描述：

  乙烯基正丁醚 、 cis-caran-trans-2-ol 在 mercury(II) diacetate 作用下， 反应 9.0h， 以45%的产率得到(+)-2-(ethenyloxy)-3,7,7-trimethylbicyclo[4.1.0]heptane
  参考文献：
  名称：

  `Inverse-Electron-Demand'Diels-Alder Reactions of (E)-3-Diazenylbut-2-enes in Water

  摘要：

  The cycloadditions of (E)-3-diazenylbul-2-enes 1 with a variety of alkenes 2-6 were carried out in water as well as in organic solvents. The reactions were always faster in heterogeneous aqueous medium than in the organic solvents. These conjugated diazenyl-alkenes behave mainly as heterodienes. and the Diels-Alder adducts are the sole or at least main reaction products. Pyrroles derived from zwitterionic [3 + 2] cycloaddition reactions were observed in some cases. The cycloaddition of 1a with (+)-2-(ethenyloxy)-3,7,7-trimethylbicycloclo[4.1.0]heptane (5) is the first example of an asymmetric 'inverse electron-demand' Diels-Alder reaction carried out in pure water.

  DOI：

  10.1002/1522-2675(20010228)84:2<513::aid-hlca513>3.0.co;2-s

文献信息

• [4 + 2] Cycloadditions of Nitroalkenes in Water. Highly Asymmetric Synthesis of Functionalized Nitronates
  作者：Francesco Fringuelli、Mizio Matteucci、Oriana Piermatti、Ferdinando Pizzo、Maria Cristina Burla

  DOI：10.1021/jo010182v

  日期：2001.6.1

  The [4 + 2] cycloadditions of (E)-2-aryl-1-cyano-1-nitroalkenes 1 with achiral and enantiopure vinyl ethers 2 and 3 carried out in sole water are reported. These reactions occur in a heterogeneous phase under mild conditions and are fast and highly stereoselective. By using(-)-N,N-dicyclohexyl-(1S)-isoborneol-10-sulfonamide as achiral auxiliary, the cycloadditions are totally asymmetric. The face selectivity is discussed in terms of the shape of the chiral auxiliary and the reactive conformation of vinyl ether.