(-)-2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-diox-5-in-4-one | 143730-05-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-diox-5-in-4-one
• 英文别名: (2R)-2-tert-butyl-6-methyl-2-(trideuteriomethyl)-1,3-dioxin-4-one
• CAS: 143730-05-6
• 化学式: C₁₀H₁₆O₃
• 分子量: 187.211
• InChiKey: TZENLWBEADVAQX-TUUHCPJJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 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：

  1,4-二氧杂螺[4.5]癸-6-烯 、 (-)-2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-diox-5-in-4-one 以 丙酮 、 乙腈 为溶剂， 反应 12.0h， 以14%的产率得到
  参考文献：
  名称：

  Photoadditions and Dialkylcuprate Additions to 2-tert-Butyl-2,6-dimethyl-1,3-dioxin-4-one and Related Heterocycles. Experimental, Ab Initio Theoretical, and X-Ray Structural Studies of Facial Selectivity and Enone Pyramidalization

  摘要：

  Preparation and ground-state reactions of 1,3-dioxinone(1), alpha,beta-unsaturated delta-lactone 4, and dihydropyranone 5 are reported. These three substrates have identical alkyl substituents but differ in the number and placement of oxygen atoms in the heterocycle. Reaction of 1 or 4 with (n-Bu)(2)CuLi leads to exclusive addition on the top face (side opposite the tert-butyl group) of the substrate while addition to 5 gives a 50:50 mixture of diastereomers. Pyramidalizations of the enone portions of 1, 4, and 5 (along with 2-cyclohexenone) have been predicted using ab initio Hartree-Fock (HF) methods with a split-valence plus polarization basis set, 6-31G*, and with the inclusion of electron correlation by Moller-Plesset perturbation theory (MP2). These predictions have been compared with the results of X-ray crystal structure determinations on related heterocycles which were present in the Cambridge Crystallographic Database. Both theoretical methods indicate that the extent of pyramidalization decreases in the following order: 1,3-dioxinones > alpha,beta-unsaturated delta-lactones > dihydropyranones > 2-cyclohexenones. This trend suggests that the facial selectivity observed in the ground-state reactions of 1, 4, and 5 is related to the extent of pyramidalization in the enone portion of these substrates. Photoaddition reactions of 1 with various cycloalkenes are also reported. The exclusive or major product in these reactions results from attack on the bottom face of 1. Thus, substrate 1 allows exclusive entry of ground-state reactants on the top face, but excited-state reactions occur exclusively or primarily on the bottom face.

  DOI：

  10.1021/ja00087a018
• 作为产物：
  描述：

  2-tert-butyl-6-methyl-2-(methyl-d3)-1,3-dioxan-4-one 在 palladium on activated charcoal N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 氢气 、 potassium carbonate 、 三乙胺 作用下， 以 四氯化碳 为溶剂， 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

文献信息

• Photoadditions and Dialkylcuprate Additions to 2-tert-Butyl-2,6-dimethyl-1,3-dioxin-4-one and Related Heterocycles. Experimental, Ab Initio Theoretical, and X-Ray Structural Studies of Facial Selectivity and Enone Pyramidalization
  作者：Michael G. Organ、Robert D. J. Froese、John D. Goddard、Nicholas J. Taylor、Gordon L. Lange

  DOI：10.1021/ja00087a018

  日期：1994.4

  Preparation and ground-state reactions of 1,3-dioxinone(1), alpha,beta-unsaturated delta-lactone 4, and dihydropyranone 5 are reported. These three substrates have identical alkyl substituents but differ in the number and placement of oxygen atoms in the heterocycle. Reaction of 1 or 4 with (n-Bu)(2)CuLi leads to exclusive addition on the top face (side opposite the tert-butyl group) of the substrate while addition to 5 gives a 50:50 mixture of diastereomers. Pyramidalizations of the enone portions of 1, 4, and 5 (along with 2-cyclohexenone) have been predicted using ab initio Hartree-Fock (HF) methods with a split-valence plus polarization basis set, 6-31G*, and with the inclusion of electron correlation by Moller-Plesset perturbation theory (MP2). These predictions have been compared with the results of X-ray crystal structure determinations on related heterocycles which were present in the Cambridge Crystallographic Database. Both theoretical methods indicate that the extent of pyramidalization decreases in the following order: 1,3-dioxinones > alpha,beta-unsaturated delta-lactones > dihydropyranones > 2-cyclohexenones. This trend suggests that the facial selectivity observed in the ground-state reactions of 1, 4, and 5 is related to the extent of pyramidalization in the enone portion of these substrates. Photoaddition reactions of 1 with various cycloalkenes are also reported. The exclusive or major product in these reactions results from attack on the bottom face of 1. Thus, substrate 1 allows exclusive entry of ground-state reactants on the top face, but excited-state reactions occur exclusively or primarily on the bottom face.
• 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.