5-Bromo-6-(bromomethyl)-2,3-dihydropyran-4-one | 178452-91-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 5-Bromo-6-(bromomethyl)-2,3-dihydropyran-4-one
• CAS: 178452-91-0
• 化学式: C₆H₆Br₂O₂
• 分子量: 269.92
• InChiKey: HNUPMZBTCUEHJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-Bromo-6-(bromomethyl)-2,3-dihydropyran-4-one 在 palladium on activated charcoal 氢气 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.33h， 生成 Diethyl 2-[(2,2-dimethyl-6-oxo-1,3-dioxin-4-yl)methyl]-2-[(4-oxo-2,3-dihydropyran-6-yl)methyl]propanedioate
  参考文献：
  名称：

  通过二氢-4-吡喃酮与1,3-二恶英-4-酮的光加成反应选择性合成螺醚和螺酮

  摘要：

  提出了一种多功能和立体选择性合成螺醚和螺环酮的方法。关键步骤基于分子内将二氢-4-吡喃酮光加成为1,3-二恶英-4-酮，随后进行片段化，得到螺醚，在Baeyer-Villager氧化后，该螺醚可提供相应的螺环酮，并保留其构型。螺旋中心。该中心的构型由在光加成步骤中手性二恶英酮的面部选择性定义。因此，该方法能够实现热力学上较不稳定的螺环酮的立体选择性合成，螺环酮通常通过依赖平衡的大多数常规方法以异构体混合物形式生产。在存在内标物的情况下，合成热力学较不稳定的螺酮，然后进行受控差向异构化，

  DOI：

  10.1016/0040-4039(96)00602-8
• 作为产物：
  描述：

  2,3-二氢-6-甲基-4H-吡喃-4-酮 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 以10%的产率得到5-Bromo-6-(dibromomethyl)-2,3-dihydropyran-4-one
  参考文献：
  名称：

  Enantioselective Synthesis of Spiro Ethers and Spiro Ketals via Photoaddition of Dihydro-4-pyrones to Chiral 1,3-Dioxin-4-ones

  摘要：

  A versatile and highly stereoselective synthesis of spiro ethers and spiro ketals is presented. The key step in the developed synthetic sequence is based on diastereoselective intramolecular photoaddition of dihydro-4-pyrones to chiral 1,3-dioxin-4-ones. Subsequent fragmentation of the produced four-membered ring provides spiro ether structures. The spiro ethers can be transformed to their corresponding spiro ketals, with retention of configuration at the spiro center, via Baeyer-Villager oxidation. The configuration of the spiro center is defined by the facial selectivity at the photocycloaddition step. Two examples of complete stereofacial selectivity were achieved. The unique and important application of the developed sequence was demonstrated in enantioselective synthesis of a less thermodynamically stable spiro ketal 43.

  DOI：

  10.1021/jo970816r

文献信息

• Stereoselective synthesis of spiroethers and spiroketals via photoaddition of dihydro-4-pyrones to 1,3-dioxin-4-ones
  作者：Nizar Haddad、Zehavit Abramovich、Igor Ruhman

  DOI：10.1016/0040-4039(96)00602-8

  日期：1996.5

  intramolecular photoaddition of dihydro-4-pyrones to 1,3-dioxin-4-ones, followed by subsequent fragmentation affording a spiroether which provides, after Baeyer-Villager oxidation, the corresponding spiroketal with complete retention of configuration at the spirocenter. The configuration of this center is defined by the facial selectivity of the chiral dioxinone at the photoaddition step. Thus, this

  提出了一种多功能和立体选择性合成螺醚和螺环酮的方法。关键步骤基于分子内将二氢-4-吡喃酮光加成为1,3-二恶英-4-酮，随后进行片段化，得到螺醚，在Baeyer-Villager氧化后，该螺醚可提供相应的螺环酮，并保留其构型。螺旋中心。该中心的构型由在光加成步骤中手性二恶英酮的面部选择性定义。因此，该方法能够实现热力学上较不稳定的螺环酮的立体选择性合成，螺环酮通常通过依赖平衡的大多数常规方法以异构体混合物形式生产。在存在内标物的情况下，合成热力学较不稳定的螺酮，然后进行受控差向异构化，
• Enantioselective Synthesis of Spiro Ethers and Spiro Ketals <i>via</i> Photoaddition of Dihydro-4-pyrones to Chiral 1,3-Dioxin-4-ones
  作者：Nizar Haddad、Igor Rukhman、Zehavit Abramovich

  DOI：10.1021/jo970816r

  日期：1997.10.1

  A versatile and highly stereoselective synthesis of spiro ethers and spiro ketals is presented. The key step in the developed synthetic sequence is based on diastereoselective intramolecular photoaddition of dihydro-4-pyrones to chiral 1,3-dioxin-4-ones. Subsequent fragmentation of the produced four-membered ring provides spiro ether structures. The spiro ethers can be transformed to their corresponding spiro ketals, with retention of configuration at the spiro center, via Baeyer-Villager oxidation. The configuration of the spiro center is defined by the facial selectivity at the photocycloaddition step. Two examples of complete stereofacial selectivity were achieved. The unique and important application of the developed sequence was demonstrated in enantioselective synthesis of a less thermodynamically stable spiro ketal 43.