(2R)-5-bromo-2-tert-butyl-6-methyl-2-(trideuteriomethyl)-1,3-dioxin-4-one | 143680-82-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R)-5-bromo-2-tert-butyl-6-methyl-2-(trideuteriomethyl)-1,3-dioxin-4-one
• CAS: 143680-82-4
• 化学式: C₁₀H₁₅BrO₃
• 分子量: 266.107
• InChiKey: FZWNPEAULYGYPZ-TUUHCPJJSA-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：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (2R)-5-bromo-2-tert-butyl-6-methyl-2-(trideuteriomethyl)-1,3-dioxin-4-one 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 生成 (-)-2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-diox-5-in-4-one
  参考文献：
  名称：

  Bromination of 2,2,6-trialkyl-1,3-dioxan-4-ones. Application of the deuterium isotope effect to the synthesis of a chiral trialkyldioxinone

  摘要：

  Free-radical bromination (2 equiv of NBS) of 2-tert-butyl-2,6-dimethyl-1,3-dioxan-4-one (6a) gives the 2-bromomethyl product 7a. By contrast, bromination of 2-tert-butyl-2-methyl-1,3-dioxan-4-one (1) is reported to occur at the 6-position. Deuterium-labeling experiments established that 7a is formed by direct substitution at the 2-methyl group of 6a and not by abstraction of H-6 followed by hydrogen atom transfer from the 2-methyl group and bromination of the resultant primary radical 12. When 2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one (13) is reacted with 4 equiv of NBS, the course of the reaction is altered dramatically and the major product formed in high yield is dioxinone 16. Thus, a trideuteriomethyl group directs bromination away from the 2-methyl site to H-6. Bromination at the 6-position followed by loss of HBr, addition of Br2, and loss of a second HBr gives 16. Dioxinone 14, a valuable substrate for asymmetric induction studies, is formed in high yield by reductive debromination of 16. When (R)-3-hydroxybutyric acid is used in the preparation of 13, optically pure (-)-14 is obtained using the sequence described.

  DOI：

  10.1021/jo00048a039
• 作为产物：
  描述：

  2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 potassium carbonate 作用下， 以 四氯化碳 为溶剂， 生成 (2R)-5-bromo-2-tert-butyl-6-methyl-2-(trideuteriomethyl)-1,3-dioxin-4-one
  参考文献：
  名称：

  Bromination of 2,2,6-trialkyl-1,3-dioxan-4-ones. Application of the deuterium isotope effect to the synthesis of a chiral trialkyldioxinone

  摘要：

  Free-radical bromination (2 equiv of NBS) of 2-tert-butyl-2,6-dimethyl-1,3-dioxan-4-one (6a) gives the 2-bromomethyl product 7a. By contrast, bromination of 2-tert-butyl-2-methyl-1,3-dioxan-4-one (1) is reported to occur at the 6-position. Deuterium-labeling experiments established that 7a is formed by direct substitution at the 2-methyl group of 6a and not by abstraction of H-6 followed by hydrogen atom transfer from the 2-methyl group and bromination of the resultant primary radical 12. When 2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one (13) is reacted with 4 equiv of NBS, the course of the reaction is altered dramatically and the major product formed in high yield is dioxinone 16. Thus, a trideuteriomethyl group directs bromination away from the 2-methyl site to H-6. Bromination at the 6-position followed by loss of HBr, addition of Br2, and loss of a second HBr gives 16. Dioxinone 14, a valuable substrate for asymmetric induction studies, is formed in high yield by reductive debromination of 16. When (R)-3-hydroxybutyric acid is used in the preparation of 13, optically pure (-)-14 is obtained using the sequence described.

  DOI：

  10.1021/jo00048a039

文献信息

• Bromination of 2,2,6-trialkyl-1,3-dioxan-4-ones. Application of the deuterium isotope effect to the synthesis of a chiral trialkyldioxinone
  作者：Gordon L. Lange、Michael G. Organ、Michael R. Roche

  DOI：10.1021/jo00048a039

  日期：1992.10

  Free-radical bromination (2 equiv of NBS) of 2-tert-butyl-2,6-dimethyl-1,3-dioxan-4-one (6a) gives the 2-bromomethyl product 7a. By contrast, bromination of 2-tert-butyl-2-methyl-1,3-dioxan-4-one (1) is reported to occur at the 6-position. Deuterium-labeling experiments established that 7a is formed by direct substitution at the 2-methyl group of 6a and not by abstraction of H-6 followed by hydrogen atom transfer from the 2-methyl group and bromination of the resultant primary radical 12. When 2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one (13) is reacted with 4 equiv of NBS, the course of the reaction is altered dramatically and the major product formed in high yield is dioxinone 16. Thus, a trideuteriomethyl group directs bromination away from the 2-methyl site to H-6. Bromination at the 6-position followed by loss of HBr, addition of Br2, and loss of a second HBr gives 16. Dioxinone 14, a valuable substrate for asymmetric induction studies, is formed in high yield by reductive debromination of 16. When (R)-3-hydroxybutyric acid is used in the preparation of 13, optically pure (-)-14 is obtained using the sequence described.