(3E,5E)-4-Methyl-6-phenyl-hexa-3,5-dien-2-ol | 170942-01-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (3E,5E)-4-Methyl-6-phenyl-hexa-3,5-dien-2-ol
• CAS: 170942-01-5
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: BIMKMIFZZBONDF-BNFZFUHLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (3E,5E)-4-Methyl-6-phenyl-hexa-3,5-dien-2-ol 在 silica gel 作用下， 以 苯 为溶剂， 反应 192.0h， 生成 (1S,3aR,4S,5S,7aS)-1,7-Dimethyl-3-oxo-5-phenyl-1,3,3a,4,5,7a-hexahydro-isobenzofuran-4-carboxylic acid phenylamide
  参考文献：
  名称：

  Highly Like-Selective [4 + 2] Cycloadditions of Chiral Dienols: The Importance of 1,3-Allylic Strain in the Hydroxy-Directed Stereocontrol

  摘要：

  The chiral open-chain dienols 3a,b, which possess 1,3-allylic strain due to the presence of a cis substituent, give with the dienophiles maleic anhydride (MA), N-phenyl maleimide (NPM), 4-phenyl- (PTAD), and 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) the corresponding [4 + 2] cycloadducts in very good yields and with high like selectivity. In contrast to previous reports on dienols without 1,3-allylic strain, the sense of diastereoselectivity does not vary with the dienophile type. The cis substituent aligns preferred conformations in the ground and transition states for which the hydrogen atom is placed in the sterically most biased inside position. Sterically and electronically controlled dienophile attack on these rotamers leads to the observed like stereochemistry. The participation of electronic features, most prominently hydroxy-directed stereocontrol, is substantiated by solvent effects in the triazolinedione cycloadditions, i.e., lower pi-facial selectivities are observed in polar solvents. The present results demonstrate the efficacy of 1,3-allylic strain in promoting conformational preferences in [4 + 2] cycloadditions with asymmetric dienols.

  DOI：

  10.1021/ja00141a010
• 作为产物：
  描述：

  (E,E)-4-methyl-6-phenyl-3,5-hexadiene-2-one 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 以85%的产率得到(3E,5E)-4-Methyl-6-phenyl-hexa-3,5-dien-2-ol
  参考文献：
  名称：

  Highly Like-Selective [4 + 2] Cycloadditions of Chiral Dienols: The Importance of 1,3-Allylic Strain in the Hydroxy-Directed Stereocontrol

  摘要：

  The chiral open-chain dienols 3a,b, which possess 1,3-allylic strain due to the presence of a cis substituent, give with the dienophiles maleic anhydride (MA), N-phenyl maleimide (NPM), 4-phenyl- (PTAD), and 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) the corresponding [4 + 2] cycloadducts in very good yields and with high like selectivity. In contrast to previous reports on dienols without 1,3-allylic strain, the sense of diastereoselectivity does not vary with the dienophile type. The cis substituent aligns preferred conformations in the ground and transition states for which the hydrogen atom is placed in the sterically most biased inside position. Sterically and electronically controlled dienophile attack on these rotamers leads to the observed like stereochemistry. The participation of electronic features, most prominently hydroxy-directed stereocontrol, is substantiated by solvent effects in the triazolinedione cycloadditions, i.e., lower pi-facial selectivities are observed in polar solvents. The present results demonstrate the efficacy of 1,3-allylic strain in promoting conformational preferences in [4 + 2] cycloadditions with asymmetric dienols.

  DOI：

  10.1021/ja00141a010