(Z)-4-methylpent-3-en-2-ol-2,5,5,5-d4 | 229022-01-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-4-methylpent-3-en-2-ol-2,5,5,5-d4
• 英文别名: (Z)-4-methyl-2,5,5,5-tetradeutriopent-3-en-2-ol；(Z)-2,5,5,5-tetradeuterio-4-methylpent-3-en-2-ol
• CAS: 229022-01-9
• 化学式: C₆H₁₂O
• 分子量: 104.129
• InChiKey: SAOXPNBHKSWHGW-QCWLUFQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  1-硝基-4-亚硝基苯 、 (Z)-4-methylpent-3-en-2-ol-2,5,5,5-d4 以 氘代氯仿 为溶剂， 反应 24.0h， 生成 、 、
  参考文献：
  名称：

  单线态氧、三唑啉二酮和亚硝基芳烃与手性氘标记的烯丙醇的烯反应：非对映选择性和区域选择性的相互依赖性揭示了对羟基方向性的机理见解

  摘要：

  单线态氧 ((1)O(2))、三唑啉二酮 (TAD) 和亚硝基芳烃，特别是 4-亚硝基苯 (ArNO) 与四取代的 1,3-烯丙基张力、手性烯丙醇 3,4-二甲基戊的烯反应-3-en-2-ol (2) 导致具有高非对映选择性的苏式构型的烯产物，这是羟基方向性的结果。氢键有利于在烯反应的早期形成苏式构型的遭遇复杂的苏式-EC。对于类似的 twix 氘标记的烯丙醇 Z-2-d(3)，在四取代醇的区域选择性中公开了 (1)O(2) 与 ArNO 和 TAD 亲烯体之间迄今尚未认识到的二分法：而对于 ArNO 和TAD，与烯丙基羟基的氢键决定了区域选择性（twix 选择性），对于（1）O（2），顺式效应占主导地位（孪生/三重选择性）。从双/双区域选择性和苏/赤非对映选择性之间的相互依赖性，已经认识到，亲烯体也可以在没有与烯丙基羟基官能团的氢键帮助的情况下从赤π面攻击烯丙醇。

  DOI：

  10.1021/ja027800p
• 作为产物：
  描述：

  (Z)-4-methylpent-3-en-2-one-5,5,5-d3 在 lithium aluminium deuteride 作用下， 生成 (Z)-4-methylpent-3-en-2-ol-2,5,5,5-d4
  参考文献：
  名称：

  三唑啉二酮与手性烯丙基醇的非对映选择性烯反应。亲羟基分子转向作用的证据

  摘要：

  PTAD与手性烯丙醇4-甲基-3-戊烯-2-醇的烯反应在非极性溶剂中表现出高的苏非对映选择性，而在极性溶剂中，非对映选择性显着降低。根据非对映异构体顺式和反叠氮基亚胺中间体的形成过程中羟基与传入的亲油体之间的导向作用来讨论这些结果。

  DOI：

  10.1016/s0040-4039(98)00207-x

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.