6-tert-butyl-5,6-dihydro-4-methoxy-6-methyl-2H-pyran-2-one | 155060-34-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 6-tert-butyl-5,6-dihydro-4-methoxy-6-methyl-2H-pyran-2-one
• 英文别名: 2-tert-butyl-4-methoxy-2-methyl-3H-pyran-6-one
• CAS: 155060-34-7
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: VVFXCXMDIKTBSN-UHFFFAOYSA-N

物化性质

• 沸点：
  309.6±42.0 °C(predicted)
• 密度：
  1.01±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  6-tert-butyl-5,6-dihydro-4-methoxy-6-methyl-2H-pyran-2-one 在 copper(l) iodide 、 三甲基氯硅烷 作用下， 生成 4β-n-butyl-6α-tert-butyl-tetrahydro-4α,6β-dimethyl-2H-pyran-2-one
  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：

  methyl 5-hydroxy-5,6,6-trimethyl-3-oxoheptanoate 在 盐酸 、 sodium hydroxide 、 硫酸 作用下， 以 氯仿 为溶剂， 反应 22.25h， 生成 6-tert-butyl-5,6-dihydro-4-methoxy-6-methyl-2H-pyran-2-one
  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

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.