(E)-2,4-dimethylpent-3-en-2-ol-5,5,5-d3 | 183295-42-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-2,4-dimethylpent-3-en-2-ol-5,5,5-d3
• 英文别名: E-2,4-dimethylpent-3-en-2-ol-5,5,5-d₃；(E)-5,5,5-trideuterio-2,4-dimethylpent-3-en-2-ol
• CAS: 183295-42-3
• 化学式: C₇H₁₄O
• 分子量: 117.164
• InChiKey: PCFLZEMUEOSJPS-HBTQZZDTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  (E)-2,4-dimethylpent-3-en-2-ol-5,5,5-d3 在 2,6-二叔丁基苯酚 、 氧气 、 tetraphenylporphyrin 作用下， 以 四氯化碳 为溶剂， 生成 5,5-Dideuterio-3-deuterioperoxy-2,4-dimethylpent-4-en-2-ol 、 3-Hydroperoxy-2-methyl-4-(trideuteriomethyl)pent-4-en-2-ol
  参考文献：
  名称：

  单线态氧与烯丙醇的烯反应立体选择性中的溶剂效应

  摘要：

  单线态氧与E -2,4-二甲基戊-3-en-2-ol-5,5,5-d 3的烯反应的立体选择性取决于溶剂。极性溶剂有利于从甲基抗醇到醇的氢提取；非极性溶剂则相反。

  DOI：

  10.1016/0040-4039(96)01621-8
• 作为产物：
  描述：

  甲基碘化镁 、 (E)-ethyl 3-methylbut-2-enoate-4,4,4-d3 生成 (E)-2,4-dimethylpent-3-en-2-ol-5,5,5-d3
  参考文献：
  名称：

  单线态氧与烯丙醇的烯反应立体选择性中的溶剂效应

  摘要：

  单线态氧与E -2,4-二甲基戊-3-en-2-ol-5,5,5-d 3的烯反应的立体选择性取决于溶剂。极性溶剂有利于从甲基抗醇到醇的氢提取；非极性溶剂则相反。

  DOI：

  10.1016/0040-4039(96)01621-8

文献信息

• Stereochemistry in the Ene Reactions of Singlet Oxygen and Triazolinediones with Allylic Alcohols. A Mechanistic Comparison
  作者：Georgios Vassilikogiannakis、Manolis Stratakis、Michael Orfanopoulos、Christopher S. Foote

  DOI：10.1021/jo990258b

  日期：1999.5.1

  The ene reaction of singlet oxygen with (Z)-4-methylpent-3-en-2-ol-2,5,5,5-d(4) (1-OH-d4) in nonpolar solvents exhibits a 90% three diastereoselectivity in the adduct derived from the major syn perepoxide intermediate, but also a moderate three diastereoselectivity in the adduct derived from the minor anti perepoxide. Photooxygenation of 2,4-dimethylpent-3-en-2-ol (2) exhibits a significant solvent dependence in the syn/anti methyl stereoselectivity, with nonpolar solvents promoting syn methyl reactivity, while polar solvents promote anti methyl reactivity. These results are in agreement with a steering effect between hydroxyl and singlet oxygen in the rate-determining step of the reaction. N-Phenyltriazolinedione addition to the chiral allylic alcohol 4-methylpent-3-en-2-ol (1-OH) is highly three diastereoselective in nonpolar solvents, with a solvent dependent variation in the threo/erythro ene products. On the other hand, the nonfunctionalized chiral alkene 2,4-dimethyl-2-hexene (1-Et) exhibits poor diastereoselectivity. Reaction of PTAD with 1-OH-d4 in nonpolar solvents, exhibits a significant three diastereoselectivity from the syn aziridinium imide intermediate, and a moderate three diastereoselectivity from the anti intermediate. These results are consonant with a steering effect between the hydroxyl and the electrophile, as proposed in the case of singlet oxygen addition to allylic alcohols 1-OH and 2. In contrast to the analogous O-1(2) ene reaction, a solvent independent ratio syn/anti similar to 50/50 was found in the addition of MTAD to 2. The intermolecular kinetic isotope effect in the reaction of 2 with MTAD (k(H)/k(D) = 1.15 +/- 0.02), is consistent with formation of the intermediate in fast step, indicative that the steering effect during the formation of aziridium imide is not important in the reaction kinetics. This energetic profile is in contrast to triazolinedione addition to the secondary allylic alcohol 1-OH, where the high three selectivity and the slight inverse kinetic isotope effect of k(H)/k(D) = 0.98 +/- 0.02 are consonant with the formation of the intermediate in the rate-determining step. An explanation for the increased reactivity of the syn methyl in the addition of MTAD to 2 (similar to 50%) is offered.
• Solvent effects in the stereoselectivity of the ene reaction of singlet oxygen with allylic alcohols
  作者：Manolis Stratakis、Michael Orfanopoulos、Christopher S. Foote

  DOI：10.1016/0040-4039(96)01621-8

  日期：1996.9

  The stereoselectivity of the ene reaction of singlet oxygen with E-2,4-dimethylpent-3-en-2-ol-5,5,5-d3 depends on solvent; polar solvents favor hydrogen abstraction from the methyl anti to the alcohol; nonpolar solvents favor the opposite.

  单线态氧与E -2,4-二甲基戊-3-en-2-ol-5,5,5-d 3的烯反应的立体选择性取决于溶剂。极性溶剂有利于从甲基抗醇到醇的氢提取；非极性溶剂则相反。