Methyl (E)-2-(hydroxymethyl)-2-pentenoate | 153996-40-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: Methyl (E)-2-(hydroxymethyl)-2-pentenoate
• 英文别名: methyl (E)-2-(hydroxymethyl)pent-2-enoate
• CAS: 153996-40-8
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: QQJPVKXQHKRSQW-GQCTYLIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl (E)-2-(hydroxymethyl)-2-pentenoate 在 吡啶 、 2,6-二甲基吡啶 、 ruthenium trichloride 、 sodium periodate 、 三氟甲磺酸酐 、 4 A molecular sieve 、 叠氮磷酸二苯酯 、 三氟化硼乙醚 、 四丁基氟化铵 、 水 、 diethylzinc 、 二异丁基氢化铝 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 四氯化碳 、 正己烷 、 二氯甲烷 、 环己烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 29.75h， 生成 (1S,2R)-1-Azidocarbonyl-2-ethyl-cyclopropanecarboxylic acid tert-butyl ester
  参考文献：
  名称：

  Charette, André B.; Côté, Bernard, Journal of the American Chemical Society, 1995, vol. 117, # 51, p. 12721 - 12732

  摘要：

  DOI：
• 作为产物：
  描述：

  Methyl (E)-2-<<(4-nitrobenzoyl)oxy>methyl>-2-pentenoate 在 甲醇 、 potassium carbonate 作用下， 反应 1.0h， 以80%的产率得到Methyl (E)-2-(hydroxymethyl)-2-pentenoate
  参考文献：
  名称：

  Synthesis of Luminacin D

  摘要：

  The total synthesis of luminacin D (1) is reported on the basis of two aldol reactions to form the carbohydrate sector, aldehyde 30. Reaction of aldehyde 30 with the aryllithium intermediate derived from aryl iodide 38, cleavage of the silyl ether, and oxidation led to keto aldehyde 41. This advanced intermediate could be converted to luminacin 1 and its 6', 8'-epimer.

  DOI：

  10.1021/jo061104g

文献信息

• Stereocontrol by Quaternary Centres: A Stereoselective Synthesis of (−)-Luminacin D
  作者：Nathan Bartlett、Leona Gross、Florent Péron、Daniel J. Asby、Matthew D. Selby、Ali Tavassoli、Bruno Linclau

  DOI：10.1002/chem.201304776

  日期：2014.3.17

  can be achieved by 1,3‐chelation‐controlled allylation of aldehydes that possess a non‐chelating α‐ether substituent, even if the α‐position is a quaternary centre and/or a spiro‐epoxide. This reaction was used as a key step in an enantioselective synthesis of the angiogenesis inhibitor luminacin D.

  通过具有非螯合α-醚取代基的醛的1,3-螯合控制的烯丙基化可以实现非常高的非对映选择性，即使α-位置为季中心和/或螺-环氧化物。该反应被用作血管生成抑制剂luminacin D的对映选择性合成中的关键步骤。
• Synthesis of Monoprotected 2-Alkylidene-1,3-propanediols by an Unusual SN2' Mitsunobu Reaction
  作者：Andre B. Charette、Bernard Cote、Sylvie Monroc、Sylvie Prescott

  DOI：10.1021/jo00126a046

  日期：1995.10

  A simple and efficient route to monoprotected (E)- and (Z)-2-alkylidene-1,3-propanediols is described. The key step involves an unusual regio- and stereoselective S(N)2' Mitsunobu reaction of substituted 3-hydroxy-2-methylenealkanoates which are readily available from a Baylis-Hillman reaction between methyl acrylate and an aldehyde. These allylic alcohols, when treated with PPh(3), a carboxylic acid, and DEAD in THF at temperatures ranging from -40 degrees C to 22 degrees C, produced the corresponding 2-alkylidene-3-hydroxypropanoate derivatives (or (E)-2-(hydroxymethyl)-3-substituted-2-alkenoate derivatives) in >70% with S(N)2':S(N)2 ratio of 22:1 to >50:1. It was found that weak and bulky carboxylic acids and low temperatures favor S(N)2' addition. The reaction conditions were effective for alkyl substituted derivatives, but the addition of Et(3)N to the Mitsunobu conditions was necessary to improve the S(N)2':S(N)2 ratios for the vinyl 19 and phenyl 20 derivatives. The monoprotected (Z)- and (E)-2-alkylidene-1,3-propanediols can be efficiently synthesized by a three-step sequence involving either a transesterification, protection, and DIBAL-H reduction (>80% overall yield) or by the chemoselective reduction, protection, and ester cleavage (67% overall yield).
• Synthesis of monoprotected 2-alkylidene-1,3-propanediols by an unusual SN2′ Mitsunobu reaction
  作者：André B. Charette、Bernard Côté

  DOI：10.1016/s0040-4039(00)91807-0

  日期：1993.10

  A simple and efficient route to monoprotected E- and Z-2-alkylidene-1,3-propanediols was developed. The key step involves an unusual regio- and stereoselective SN2' Mitsunobu reaction of substituted 3-hydroxy-2-methylenealkenoate.
• US4810798A
  申请人：——

  公开号：US4810798A

  公开（公告）日：1989-03-07