(4aR,8aS)-2,2-Dimethyl-4,4a,8,8a-tetrahydro-benzo[1,3]dioxin-5-one | 328926-63-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4aR,8aS)-2,2-Dimethyl-4,4a,8,8a-tetrahydro-benzo[1,3]dioxin-5-one
• 英文别名: (4aR,8aS)-2,2-dimethyl-4,4a,8,8a-tetrahydro-1,3-benzodioxin-5-one
• CAS: 328926-63-2
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: LLQJIIVTUVEDGA-CBAPKCEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• 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：

  (4aR,8aS)-2,2-Dimethyl-4,4a,8,8a-tetrahydro-benzo[1,3]dioxin-5-one 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride 、 4-甲基苯磺酸吡啶 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 [(1R,5S,6R)-5-hydroxy-6-(hydroxymethyl)cyclohex-2-en-1-yl] acetate
  参考文献：
  名称：

  Enantioselective Synthesis and Conformational Study of Cyclohexene Carbocyclic Nucleosides

  摘要：

  Enantioselective synthesis of a new family of unsaturated six-membered carbocyclic nucleosides using (R)-(-)-can one as starting material is described. Introduction of the base moiety via Mitsunobu reaction proceeded regio- and stereoselectively and with good chemical yield, while the Pd-coupling approach failed. H-1 NMR study and molecular modeling show the adenine compound exists in an equilibrium of H-3(2) and H-2(3) conformers (ratio 7:3) in favor of the 3'-endo half-chair conformation, with the base oriented in a pseudoaxial position. This conformational preference can be explained by the pi --> sigma*(C1')-(N1) interaction involving the antibonding orbital of the C1'-N bond.

  DOI：

  10.1021/jo9908288
• 作为产物：
  描述：

  (1S,2R,3R,5S)-3-benzyloxy-5-(tert-butyldimethylsilyloxy)-2-hydroxymethyl-cyclohexanol 在 potassium fluoride 、 重铬酸吡啶 、 18-冠醚-6 、 甲酸铵 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 32.0h， 生成 (4aR,8aS)-2,2-Dimethyl-4,4a,8,8a-tetrahydro-benzo[1,3]dioxin-5-one
  参考文献：
  名称：

  Enantioselective Synthesis and Conformational Study of Cyclohexene Carbocyclic Nucleosides

  摘要：

  Enantioselective synthesis of a new family of unsaturated six-membered carbocyclic nucleosides using (R)-(-)-can one as starting material is described. Introduction of the base moiety via Mitsunobu reaction proceeded regio- and stereoselectively and with good chemical yield, while the Pd-coupling approach failed. H-1 NMR study and molecular modeling show the adenine compound exists in an equilibrium of H-3(2) and H-2(3) conformers (ratio 7:3) in favor of the 3'-endo half-chair conformation, with the base oriented in a pseudoaxial position. This conformational preference can be explained by the pi --> sigma*(C1')-(N1) interaction involving the antibonding orbital of the C1'-N bond.

  DOI：

  10.1021/jo9908288

文献信息

• CARBOCYCLIC NUCLEOSIDES AND PROCESS FOR OBTAINING SUCH
  申请人：Stichting REGA V.Z.W.

  公开号：EP1210347B1

  公开（公告）日：2004-06-23
• Enantioselective Synthesis and Conformational Study of Cyclohexene Carbocyclic Nucleosides
  作者：Jing Wang、Piet Herdewijn

  DOI：10.1021/jo9908288

  日期：1999.10.1

  Enantioselective synthesis of a new family of unsaturated six-membered carbocyclic nucleosides using (R)-(-)-can one as starting material is described. Introduction of the base moiety via Mitsunobu reaction proceeded regio- and stereoselectively and with good chemical yield, while the Pd-coupling approach failed. H-1 NMR study and molecular modeling show the adenine compound exists in an equilibrium of H-3(2) and H-2(3) conformers (ratio 7:3) in favor of the 3'-endo half-chair conformation, with the base oriented in a pseudoaxial position. This conformational preference can be explained by the pi --> sigma*(C1')-(N1) interaction involving the antibonding orbital of the C1'-N bond.