(Z)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester | 340175-42-0

• 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: (Z)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester
• 英文别名: methyl (Z)-4-[tert-butyl(dimethyl)silyl]oxypent-2-enoate
• CAS: 340175-42-0
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: QZPVVLFJUCQVDF-HJWRWDBZSA-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：

  N-benzylmethylene nitrone 、 (Z)-4-(tert-Butyl-dimethyl-silanyloxy)-pent-2-enoic acid methyl ester 在 4 A molecular sieve 作用下， 以 苯 为溶剂， 生成 (4S,5R)-2-Benzyl-4-[(S)-1-(tert-butyl-dimethyl-silanyloxy)-ethyl]-isoxazolidine-5-carboxylic acid methyl ester 、 (4R,5S)-2-Benzyl-5-[(S)-1-(tert-butyl-dimethyl-silanyloxy)-ethyl]-isoxazolidine-4-carboxylic acid methyl ester 、 (4R,5S)-2-Benzyl-5-[(R)-1-(tert-butyl-dimethyl-silanyloxy)-ethyl]-isoxazolidine-4-carboxylic acid methyl ester
  参考文献：
  名称：

  静电相互作用在硝酮与手性烯丙基醚的立体选择性 1,3-偶极环加成反应中的重要性：实验和力场方法

  摘要：

  研究了甲醛N-苄基硝酮与β'-烷氧基-和γ-烷氧基-α,β-不饱和酯的1,3-偶极环加成反应。基于对内部烷氧基理论的解释，这些反应的立体化学结果很好地合理化，强调了反应 TS 中的静电相互作用。先前开发的用于评估氧化腈环加成对手性烯烃的立体选择的力场方法已成功扩展到硝酮反应。

  DOI：

  10.1002/(sici)1099-0690(199809)1998:9<1823::aid-ejoc1823>3.0.co;2-h
• 作为产物：
  描述：

  (S)-(-)-ethyl 2-(tert-butyldimethylsilyloxy)propanoate 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 3.33h， 生成 (Z)-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

文献信息

• Conformations of Allylic Fluorides and Stereoselectivities of Their Diels−Alder Cycloadditions
  作者：Danielle Grée、Laurent Vallerie、René Grée、Loic Toupet、Ilyas Washington、Jean-Pierre Pelicier、Mercedes Villacampa、José María Pérez、K. N. Houk

  DOI：10.1021/jo0016024

  日期：2001.4.1

  The preparations of new allylic fluorides from the corresponding alcohols are reported. Conformational analysis is achieved by comparison of experimental NMR measurements with theoretical (B3LYP) calculations of relative energies of conformers and J(H,H) and J(H,F) coupling constants. The Diels-Alder reactions of allylic fluorides are investigated experimentally and theoretically. The stereoselectivities

  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。