5-Bromo-6-bromomethyl-2-tert-butyl-[1,3]dioxin-4-one | 196867-29-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: 5-Bromo-6-bromomethyl-2-tert-butyl-[1,3]dioxin-4-one
• 英文别名: 5-Bromo-6-(bromomethyl)-2-tert-butyl-1,3-dioxin-4-one
• CAS: 196867-29-5
• 化学式: C₉H₁₂Br₂O₃
• 分子量: 328.0
• InChiKey: WFGLZORJVUXSTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-Bromo-6-bromomethyl-2-tert-butyl-[1,3]dioxin-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 2-(2-tert-Butyl-6-oxo-6H-[1,3]dioxin-4-ylmethyl)-2-(4-oxo-5,6-dihydro-4H-pyran-2-ylmethyl)-malonic acid diethyl ester
  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
• 作为产物：
  描述：

  2-tert-butyl-6-methyl-1,3-dioxin-4-one 在 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 作用下， 以 四氯化碳 为溶剂， 以70%的产率得到5-Bromo-6-bromomethyl-2-tert-butyl-[1,3]dioxin-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

• 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.