4-(2'-Methyl-1'-cyclohexenyl)-2-buten-1-ol | 155258-61-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(2'-Methyl-1'-cyclohexenyl)-2-buten-1-ol
• 英文别名: (E)-4-(2-methylcyclohexen-1-yl)but-2-en-1-ol
• CAS: 155258-61-0
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: WZLNUJKDCACAQL-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(2'-Methyl-1'-cyclohexenyl)-2-buten-1-ol 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二乙酯 、 4 A molecular sieve 作用下， 以 异辛烷 、 二氯甲烷 为溶剂， 反应 4.0h， 以80%的产率得到[(2S,3S)-3-(2-Methyl-cyclohex-1-enylmethyl)-oxiranyl]-methanol
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.

  DOI：

  10.1021/jo00085a037
• 作为产物：
  描述：

  methyl (E)-4-(2-methylcyclohexen-1-yl)but-2-enoate 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以81%的产率得到4-(2'-Methyl-1'-cyclohexenyl)-2-buten-1-ol
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.

  DOI：

  10.1021/jo00085a037

文献信息

• Lee Eun, Lee Yong Rok, Moon Bongjin, Kwon Ohyun, Shim Mi Seong, Yun Jae S+, J. Org. Chem, 59 (1994) N 6, S 1444-1456
  作者：Lee Eun, Lee Yong Rok, Moon Bongjin, Kwon Ohyun, Shim Mi Seong, Yun Jae S+

  DOI：——

  日期：——
• Oxyanion Orientation in Anionic Oxy-Cope Rearrangements
  作者：Eun Lee、Yong Rok Lee、Bongjin Moon、Ohyun Kwon、Mi Seong Shim、Jae Sook Yun

  DOI：10.1021/jo00085a037

  日期：1994.3

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.