(3'aR,4'S)-4'-tert-butoxydispiro[cyclopropane-1,2'-(hexahydropyrrolo[1,2-b]isoxazole)-3',1''-cyclopropane] | 250226-51-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (3'aR,4'S)-4'-tert-butoxydispiro[cyclopropane-1,2'-(hexahydropyrrolo[1,2-b]isoxazole)-3',1''-cyclopropane]
• CAS: 250226-51-8
• 化学式: C₁₄H₂₃NO₂
• 分子量: 237.342
• InChiKey: TTXRGNWDAZDTQG-QWRGUYRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3'aR,4'S)-4'-tert-butoxydispiro[cyclopropane-1,2'-(hexahydropyrrolo[1,2-b]isoxazole)-3',1''-cyclopropane] 在 三氟乙酸 作用下， 以 xylene 为溶剂， 反应 10.0h， 生成 (1'S,8a'R)-1'-hydroxyspiro(cyclopropane-1,8'octahydroindolizin)-7'-one
  参考文献：
  名称：

  Studies on the Synthesis of Aza Analogues of Illudins by Cycloadditions to Highly Strained Methylenecyclopropanes

  摘要：

  A series of 3-spirocyclopropane-tetrahydropyrid-4-ones has been synthesized by the method consisting of nitrone cycloaddition to bicyclopropylidene and thermal rearrangement of the adducts. Regioisomeric 5-spirocyclopropanetetrahydropyrid-4-ones and 5-spirocyclopropanedihydropyrid-4 ones were instead obtained by cycloaddition of nitrones and nitrile oxides, respectively, to methylenespiropentane, followed by thermal rearrangement. Methylenedispiro[2.0.2.1]heptane gave, in turn, 5,6-bis(spirocyclopropane)dihydropyrid-4 The new compounds were prepared as simple aza analogues of the cytotoxic natural products illudins and ptaquiloside in order to study their activity in cleaving a DNA plasmid. The activities shown by several of the compounds are moderate, but from a comparative qualitative analysis of the results a useful structure-activity relationship for this new class of compounds could be derived.

  DOI：

  10.1021/jo990873f
• 作为产物：
  描述：

  环亚丙基环丙烷 、 (4S)-4-tert-butoxy-3,4-dihydro-2H-pyrrole 1-oxide 以 苯 为溶剂， 反应 48.0h， 以80%的产率得到(3'aR,4'S)-4'-tert-butoxydispiro[cyclopropane-1,2'-(hexahydropyrrolo[1,2-b]isoxazole)-3',1''-cyclopropane]
  参考文献：
  名称：

  Studies on the Synthesis of Aza Analogues of Illudins by Cycloadditions to Highly Strained Methylenecyclopropanes

  摘要：

  A series of 3-spirocyclopropane-tetrahydropyrid-4-ones has been synthesized by the method consisting of nitrone cycloaddition to bicyclopropylidene and thermal rearrangement of the adducts. Regioisomeric 5-spirocyclopropanetetrahydropyrid-4-ones and 5-spirocyclopropanedihydropyrid-4 ones were instead obtained by cycloaddition of nitrones and nitrile oxides, respectively, to methylenespiropentane, followed by thermal rearrangement. Methylenedispiro[2.0.2.1]heptane gave, in turn, 5,6-bis(spirocyclopropane)dihydropyrid-4 The new compounds were prepared as simple aza analogues of the cytotoxic natural products illudins and ptaquiloside in order to study their activity in cleaving a DNA plasmid. The activities shown by several of the compounds are moderate, but from a comparative qualitative analysis of the results a useful structure-activity relationship for this new class of compounds could be derived.

  DOI：

  10.1021/jo990873f

文献信息

• Synthesis of α-Cyclopropyl-β-homoprolines
  作者：Franca M. Cordero、Maria Salvati、Carolina Vurchio、Armin de Meijere、Alberto Brandi

  DOI：10.1021/jo9004684

  日期：2009.6.5

  induced thermal fragmentative rearrangement. With the use of enantiopure pyrroline N-oxides derived from easily available chiral pool molecules, β-homoprolines were formed with high stereocontrol. The incorporation of one of these new cyclic β-amino acids into a simple tripeptide was also evaluated. In particular, the sterically hindered nitrogen atom of the highly substituted pyrrolidine 30 was smoothly

  1-（2-吡咯烷基）环丙烷羧酸（α-环丙基-β-脯氨酸）的制备方法是：将环硝酮与1,3-偶极环加成到双环亚丙基上，然后由三氟乙酸引起的热裂解重排。使用衍生自易于获得的手性库分子的对映体纯的吡咯啉N-氧化物，可形成具有高度立体控制的β-高脯氨酸。还评估了将这些新的环状β-氨基酸之一掺入简单的三肽中。特别地，通过中间形成混合酸酐，高度取代的吡咯烷30的位阻氮原子被平滑地酰化。
• 3-Spirocyclopropanedihydro- and -tetrahydropyridin-4-ones from Nitrone Cycloadducts of Bicyclopropylidene via 1-(1′-Aminomethylcyclopropyl)cyclopropanol under PdII Catalysis
  作者：Julia Revuelta、Stefano Cicchi、Armin de Meijere、Alberto Brandi

  DOI：10.1002/ejoc.200700912

  日期：2008.2

  A series of 3-spirocyclopropanedihydro- and -tetrahydropyrid-4-ones have been synthesized by nitrone cycloaddition to 1,1′-bicyclopropylidene (BCP), chemoselective reduction of the N–O bond of the isoxazolidine ring, and PdII-catalyzed cascade rearrangement of the β-aminocyclopropanol derivatives into the final products. The new tetrahydropyridone derivatives were also prepared by thermal rearrangement

  通过硝酮环加成到 1,1'-双环亚丙基 (BCP)、异恶唑烷环的 N-O 键的化学选择性还原和 PdII 催化的级联重排合成了一系列 3-螺环丙烷二氢和 -四氢吡啶-4-酮β-氨基环丙醇衍生物转化为最终产品。新的四氢吡啶酮衍生物也是通过异恶唑烷的热重排制备的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Studies on the Synthesis of Aza Analogues of Illudins by Cycloadditions to Highly Strained Methylenecyclopropanes
  作者：Chiara Zorn、Beatrice Anichini、Andrea Goti、Alberto Brandi、Sergei I. Kozhushkov、Armin de Meijere、Lorenzo Citti

  DOI：10.1021/jo990873f

  日期：1999.10.1

  A series of 3-spirocyclopropane-tetrahydropyrid-4-ones has been synthesized by the method consisting of nitrone cycloaddition to bicyclopropylidene and thermal rearrangement of the adducts. Regioisomeric 5-spirocyclopropanetetrahydropyrid-4-ones and 5-spirocyclopropanedihydropyrid-4 ones were instead obtained by cycloaddition of nitrones and nitrile oxides, respectively, to methylenespiropentane, followed by thermal rearrangement. Methylenedispiro[2.0.2.1]heptane gave, in turn, 5,6-bis(spirocyclopropane)dihydropyrid-4 The new compounds were prepared as simple aza analogues of the cytotoxic natural products illudins and ptaquiloside in order to study their activity in cleaving a DNA plasmid. The activities shown by several of the compounds are moderate, but from a comparative qualitative analysis of the results a useful structure-activity relationship for this new class of compounds could be derived.