ethyl (Z)-3-methyl-2-<4-(2)H3>butenoate | 123753-31-1

• 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: ethyl (Z)-3-methyl-2-<4-(2)H3>butenoate
• 英文别名: ethyl (Z)-[4,4,4-(2)H3]-3-methyl-2-butenoate；(Z)-ethyl 3-methylbut-2-enoate-4,4,4-d3；ethyl (Z)-3-methylbut-2-enoate-4,4,4-d3；ethyl (Z)-3-methyl-2-(4-(2)H3)butenoate；ethyl (Z)-4,4,4-trideuterio-3-methylbut-2-enoate
• CAS: 123753-31-1
• 化学式: C₇H₁₂O₂
• 分子量: 131.147
• InChiKey: UTXVCHVLDOLVPC-RDCXZEQLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl (Z)-3-methyl-2-<4-(2)H3>butenoate 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以73%的产率得到(Z)-3-methyl-2-<4-(2)H3>butenol
  参考文献：
  名称：

  Shibuya; Chou; Fountoulakis, Journal of the American Chemical Society, 1990, vol. 112, # 1, p. 297 - 304

  摘要：

  DOI：
• 作为产物：
  描述：

  1-(ethoxycarbonyl)-acetonylidenetriphenylphosphorane 在 copper(l) iodide 作用下， -69.0~280.0 ℃ 、1.2 kPa 条件下， 反应 4.08h， 生成 ethyl (Z)-3-methyl-2-<4-(2)H3>butenoate
  参考文献：
  名称：

  Shibuya; Chou; Fountoulakis, Journal of the American Chemical Society, 1990, vol. 112, # 1, p. 297 - 304

  摘要：

  DOI：

文献信息

• Nickel-Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates
  作者：Haifeng Chen、Xiao Jia、Yingying Yu、Qun Qian、Hegui Gong

  DOI：10.1002/anie.201705521

  日期：2017.10.9

  of all C(sp3) quaternary centers has been successfully achieved under Ni‐catalyzed cross‐electrophile coupling of allylic carbonates with unactivated tertiary alkyl halides. For allylic carbonates bearing C1 or C3 substituents, the reaction affords excellent regioselectivity through the addition of alkyl groups to the unsubstituted allylic carbon terminus. The allylic alkylation method also exhibits

  在烯丙基碳酸酯与未活化叔烷基卤化物的镍催化交叉亲电子偶联下，已成功实现了所有C（sp 3）季铵盐中心的构建。对于带有C1或C3取代基的烯丙基碳酸酯，该反应通过向未取代的烯丙基碳末端加成烷基而提供了优异的区域选择性。烯丙基烷基化方法还具有出色的官能团相容性，并提供具有高E 选择性的产品。
• 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.
• Synthesis of Deuterium-Labeled Derivatives of Dimethylallyl Diphosphate
  作者：Hirekodathakallu V. Thulasiram、Richard M. Phan、Susan B. Rivera、C. Dale Poulter

  DOI：10.1021/jo052384n

  日期：2006.2.1

  Short practical syntheses for five deuterium-labeled derivatives of dimethylallyl diphosphate (DMAPP) useful for enzymological studies are reported. These include the preparation of the Cl-labeled derivatives (R)-[1-H-2]3-methylbut-2-enyl diphosphate ((R)-[1-H-2]1-OPP) and (S)-[1-H-2]3-methylbut-2-enyl diphosphate ((S)-[1-H-2]1-OPP), the C2-labeled derivative [2-H-2]3-methylbut-2-enyl diphosphate ([2-H-2]1-OPP), and the methyl-labeled derivatives (E)-[4,4,4-H-2(3)]3-methylbut-2-enyl diphosphate ((E)-[4,4,4-H-2(3)]1-OPP) and (Z)-[4,4,4-H-2(3)]3-methyl-but-2-enyl diphosphate ((Z)[4,4,4-H-2(3)]1-OPP).
• SHIBUYA, M.;CHOU, H. -M.;FOUNTOULAKIS, M.;HASSAM, S.;KIM, S. -U.;KOBAYASH+, J. AMER. CHEM. SOC., 112,(1990) N, C. 297-304
  作者：SHIBUYA, M.、CHOU, H. -M.、FOUNTOULAKIS, M.、HASSAM, S.、KIM, S. -U.、KOBAYASH+

  DOI：——

  日期：——