ethyl (2E,4S)-4-methoxypent-2-enoate | 152458-92-9

• 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 (2E,4S)-4-methoxypent-2-enoate
• 英文别名: Ethyl 4-methoxy-2(E)-pentenoate；ethyl (S)-4-methoxypent-2-enoate；(E)-(S)-4-methoxypent-2-enoic acid ethyl ester；ethyl (E,4S)-4-methoxypent-2-enoate
• CAS: 152458-92-9
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: DURDPOVNAVXPLS-XPPMVYLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  ethyl (2E,4S)-4-methoxypent-2-enoate 在 双(乙腈)氯化钯(II) sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 29.5h， 生成 (3R,4S)-3-(trichloromethylcarbonylamino)-4-(methoxy)pent-1-ene
  参考文献：
  名称：

  高立体选择性醚指导的钯催化氮杂-克莱森重排。

  摘要：

  使用相邻的醚基团来指导钯（II）催化剂的面部配位，已实现了高度立体选择性的烯丙基三氯乙亚氨酸酯重整为烯丙基三氯酰胺。

  DOI：

  10.1039/b501346c
• 作为产物：
  描述：

  (S)-2-methoxypropanal 、 乙氧甲酰基亚甲基三苯基膦 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 ethyl (2E,4S)-4-methoxypent-2-enoate
  参考文献：
  名称：

  Conformational study of chiral alkenes: the influence of protective groups on the relative stability of ground-state rotational isomers

  摘要：

  A variable temperature NMR study shows that a protective group on the hydroxy function of a chiral allylic alcohol can either enhance or counter the influence of the vinyl substituent on the ground-state (GS) conformations. If the allylic hydroxy is protected as a methyl ether, the CH-eclipsed form I becomes favored to a greater degree for normal chiral alkenes. Furthermore, conformer I becomes preferred even for the gamma-hydroxy-alpha,beta-unsaturated esters, which normally favor the CO-eclipsed form (II). On the other hand, the tert-butyldimethylsilyl (TBDMS) ether enhances the preference for conformer II for the gamma-hydroxy-alpha,beta-unsaturated esters and diminishes the preference for the CH-eclipsed form of normal chiral alkenes. These facts are explained by the size of the allylic oxygen lone pairs.

  DOI：

  10.1021/jo00077a023

文献信息

• Synthesis of 3-Fluorofuran-2(5H)-ones Based onZ/E Photoisomerisation and Cyclisation of 2-Fluoro-4-hydroxybut-2-enoates
  作者：Karel Pomeisl、Jan Čejka、Jaroslav Kvíčala、Oldřich Paleta

  DOI：10.1002/ejoc.200700439

  日期：2007.12

  some (E)- and (Z)-2-fluoroalk-2-enoates prepared from the corresponding 2-hydroxycarbonyl compounds and ethyl 2-(diethoxyphosphoryl)-2-fluoroacetate have been transformed in high conversions into the target 3-fluorofuran-2(5H)-ones by an efficient Z/E photoisomerisation of noncyclisable Z isomers followed by acid-catalysed cyclisation. In contrast, the acid-catalysed deprotection of ethyl (E)- and

  由相应的 2-羟基羰基化合物和 2-(二乙氧基磷酰基)-2-氟乙酸乙酯制备的一些 (E)- 和 (Z)-2-fluoroalk-2-enoates 的混合物已以高转化率转化为目标 3-氟呋喃-2(5H)-ones 通过对不可环化的 Z 异构体进行有效的 Z/E 光异构化，然后进行酸催化环化。相反，乙基 (E)- 和 (Z)-4-[叔丁基（二甲基）甲硅烷氧基]-2-氟-4-苯基丁-2-烯酸酯的酸催化脱保护导致乙烯基氟的置换，提供(E)-2-氧代-4-苯基丁-3-烯酸乙酯。3-氟-4-苯基呋喃-2(5H)-one 转化为 2-[叔丁基（二甲基）甲硅烷氧基]-3-氟-5-甲基呋喃，作为一种新型的氟化结构单元。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Ether-directed diastereoselectivity in catalysed Overman rearrangement: comparative studies of metal catalysts
  作者：Ieva Jaunzeme、Aigars Jirgensons

  DOI：10.1016/j.tet.2008.03.099

  日期：2008.6

  Ether-directed diastereoselectivity in Overman rearrangement of delta-methoxy and delta-TBDMSO substituted allylic trichloroacetimidates has been explored using PtCl2, PtCl4, AuCl and AuCl3 catalysts in comparison with commonly used Pd(II) catalysts. For both substrates the use of PtCl2 catalyst gave notably improved anti/syn-ratio of 1,2-aminoalcohol derivatives (anti/syn=11:1 for 5-methoxy; 6:1 for delta-TBDMSO) compared to all metal catalysts known to promote Overman rearrangement. Formation of 2-trichloromethyloxazoline was observed as a dominant side reaction in the metal catalysed rearrangement of a-methoxy substituted allylic trichloroacetimidates considerably reducing the yield of the desired product. This side reaction was suppressed when delta-TBDMS-ether was used as a directing group. (C) 2008 Elsevier Ltd. All rights reserved.
• Conformational Studies of Chiral .alpha.,.beta.-Unsaturated Aldehydes
  作者：Benjamin W. Gung、Melinda S. Gerdeman、Rebecca A. Fouch、Mark A. Wolf

  DOI：10.1021/jo00094a043

  日期：1994.7

  The conformational profiles for chiral alpha,beta-unsaturated aldehydes have been studied by a combination of ab initio MO methods and the variable-temperature MMR technique. The s-trans rotational isomer around the C-sp2-C-sp2 single bond is more stable than the s-cis conformer by similar to 500 cal/mol in chloroform. This difference is 950 cal/mol according to ab initio calculations at the MP2/6-31G* level of theory. The silyl ethers, 3a-d, prefer the C-O eclipsed form while the methyl ethers, 6a-d, favor the C-H eclipsed conformation for rotations around the C-sp3-C-sp2 bond.