(E)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester | 340175-40-8

• 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: (E)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester
• 英文别名: methyl (E)-4-[tert-butyl(dimethyl)silyl]oxypent-2-enoate
• CAS: 340175-40-8
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: QZPVVLFJUCQVDF-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.13
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester 在 Amberlyst 15 作用下， 以 水 、 丙酮 为溶剂， 反应 3.0h， 以75%的产率得到methyl (E)-4-hydroxypent-2-enoate
  参考文献：
  名称：

  烯丙基氟化物的构象及其狄尔斯-阿尔德环加成反应的立体选择性。

  摘要：

  据报道由相应的醇制备新的烯丙基氟化物。构象分析是通过将实验NMR测量值与构象子相对能量以及J（H，H）和J（H，F）耦合常数的理论（B3LYP）计算进行比较而实现的。对烯丙基氟化物的狄尔斯-阿尔德反应进行了实验和理论研究。反应的立体选择性通过NMR分析确定，在一种情况下通过X射线晶体学测定。基于过渡态建模的立体选择性理论预测与实验吻合良好。报告了烯丙基氟化物和过渡态构象的理论模型。

  DOI：

  10.1021/jo0016024
• 作为产物：
  描述：

  三甲基膦酰基乙酸酯 、 2-tert-butyldimethylsilyloxypropanal 在 sodium hydride 作用下， 生成 (Z)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester 、 (E)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester
  参考文献：
  名称：

  Highly Diastereoselective Conjugate Addition of Lithium Dialkylamides to α,β-Unsaturated Esters Having a Chiral Center at the γ-Position

  摘要：

  The conjugate addition of lithium amides 2 to tert-butyl 4-(OR)-substituted-2-pentenoates 1 produced a mixture of the syn-and anti-amino esters (3 and 4) in high yields. Sterically bulky OR groups, such as trityloxy and tert-butyldiphenylsilyloxy, gave the syn diastereomer 3 either exclusively or predominantly. The syn-selectivity may be explained by a modified Felkin-Anh model. The use of tert-butyldimethylsilyloxy as an OR group afforded a nearly 1:1 mixture of diastereoisomers, and the use of the smallest MeO group produced a 63:37 mixture of the syn 3 and anti isomer 4. The presence of Me group at the alpha-position (C-2 position) of the enoate enhanced the syn diastereoselectivity up to 100%; the conjugate addition to tert-butyl 4-methoxy-2-methyl-2-pentenoate (17) gave the syn-isomer 18 exclusively. This enhancement may be explained by the combination of chelation and allylic strain model 19 in which the smallest H orients inside to avoid an allylic strain. A phenyl group at the gamma-position enhanced the anti selectivity in the case of gamma-alkoxy-alpha,beta-enoates such as isopropyl 4-[(tert-butyldimethylsilyl)oxy]-4-phenyl-2-buteonoate (20), and in the case of gamma-alkyl-alpha,beta-enoates such as tert-butyl 4-phenyl-2-pentenoate (27).

  DOI：

  10.1021/jo970435d