4α-tert-butyl-1α,7β,8α-trihydro-2β-methyl-4β-(deuteriomethyl)-3,5-dioxa-9α,9β-(ethylenedioxy)-6-oxotricyclo<6.4.0.0^2,7>dodecane | 155156-34-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4α-tert-butyl-1α,7β,8α-trihydro-2β-methyl-4β-(deuteriomethyl)-3,5-dioxa-9α,9β-(ethylenedioxy)-6-oxotricyclo<6.4.0.0^2,7>dodecane
• 英文别名: 4α-tert-butyl-1α,7β,8α-trihydro-2β-methyl-4β-(deuteriomethyl)-3,5-dioxa-9α,9β-(ethylenedioxy)-6-oxotricyclo[6.4.0.0^2,7]dodecane；(1'S,2'R,4'R,7'S,8'R)-4'-tert-butyl-2'-methyl-4'-(trideuteriomethyl)spiro[1,3-dioxolane-2,9'-3,5-dioxatricyclo[6.4.0.02,7]dodecane]-6'-one
• CAS: 155156-34-6
• 化学式: C₁₈H₂₈O₅
• 分子量: 327.393
• InChiKey: BLBKEQHKGVKHIP-JSQRMDMKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4α-tert-butyl-1α,7β,8α-trihydro-2β-methyl-4β-(deuteriomethyl)-3,5-dioxa-9α,9β-(ethylenedioxy)-6-oxotricyclo<6.4.0.0^2,7>dodecane 在 盐酸 、 二异丁基氢化铝 作用下， 生成 7β-acetyl-6β-(formylmethyl)-6α,7α-dihydro-1,4-dioxaspiro<4.5>decane 、 7α-acetyl-6β-(formylmethyl)-6α,7β-dihydro-1,4-dioxaspiro<4.5>decane
  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：

  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

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.