(Z)-4-methylpent-3-en-2-one-5,5,5-d3 | 207456-85-7

• 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-one-5,5,5-d3
• 英文别名: (Z)-4-methylpent-3-en-2-one-5,5,5-d₃；(Z)-5,5,5-trideuterio-4-methylpent-3-en-2-one
• CAS: 207456-85-7
• 化学式: C₆H₁₀O
• 分子量: 101.121
• InChiKey: SHOJXDKTYKFBRD-DWPBTMLMSA-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：
  0.5
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-4-methylpent-3-en-2-one-5,5,5-d3 在 lithium aluminium deuteride 作用下， 以 丙酮 为溶剂， 生成 1-[(3R,4S)-4-deuterio-4-hydroxy-2-(trideuteriomethyl)pent-1-en-3-yl]-4-phenyl-1,2,4-triazolidine-3,5-dione
  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
• 作为产物：
  描述：

  乙酰丙酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 sodium hydride 作用下， 以 乙醚 为溶剂， 反应 6.0h， 生成 (Z)-4-methylpent-3-en-2-one-5,5,5-d3
  参考文献：
  名称：

  Stereochemistry in the Ene Reactions of Singlet Oxygen and Triazolinediones with Allylic Alcohols. A Mechanistic Comparison

  摘要：

  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.

  DOI：

  10.1021/jo990258b

文献信息

• Isotope Effects and <i>syn</i> Selectivity in the Ene Reaction of Triazolinedione with Conjugated Enones:  Aziridinium Imide or an Open Intermediate Mechanism?
  作者：Georgios Vassilikogiannakis、Manolis Stratakis、Michael Orfanopoulos

  DOI：10.1021/ol000109b

  日期：2000.7.1

  The ene reaction of 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) with phorone-d(6) (5-d(6)) shows an inverse beta-secondary isotope effect and with mesityl oxide-d(3) (7-d(3)) proceeds with 93% syn selectivity. These results are consistent with a mechanism involving the formation of an aziridinium imide intermediate in the rate-determining step. An open biradical or dipolar intermediate is excluded by

  4-甲基-1,2,4-三唑啉-3,5-二酮（MTAD）与佛尔酮-d（6）（5-d（6））的烯键反应显示出反向的β-次级同位素效应和异丁烯氧化物-d（3）（7-d（3））的合成选择性为93％。这些结果与在速率确定步骤中涉及形成叠氮化im中间体的机理一致。开放的双自由基或偶极中间体被它们排除在外。