(E)-4-methyl-5-oxopent-3-enoic acid methyl ester | 155688-25-8

• 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-methyl-5-oxopent-3-enoic acid methyl ester
• 英文别名: methyl (E)-4-methyl-5-oxopent-3-enoate
• CAS: 155688-25-8
• 化学式: C₇H₁₀O₃
• 分子量: 142.155
• InChiKey: NSRVKVCITKQGFT-ZZXKWVIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-4-methyl-5-oxopent-3-enoic acid methyl ester 在 4-二甲氨基吡啶 、 正丁基锂 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 1.5h， 生成 (2E,4E)-methyl 4-methyl-5-(((E)-3-(p-tolyl)acryloyl)oxy)penta-2,4-dienoate
  参考文献：
  名称：

  Enantioselective All-Carbon (4+2) Annulation by N-Heterocyclic Carbene Catalysis

  摘要：

  The enantioselective vinylogous Michael/aldol cascade is an underdeveloped approach to cyclohexenes. Herein we describe a highly enantioselective (most >= 98:2 er) and diastereoselective (all >= 15:1 dr) N-heterocyclic carbene catalyzed cycloisomerization of acyclic dienyl esters to cyclohexyl beta-lactones. Derivatizations avail cyclohexenes bearing four contiguous stereogenic centers, while mechanistic studies support olefin isomerization prior to cyclization.

  DOI：

  10.1021/ja508542n
• 作为产物：
  描述：

  o-diphenylphosphanylbenzoic acid 1-methoxycarbonylmethylallyl ester 、 一氧化碳 在 (acetylacetonato)dicarbonylrhodium (l) 、 potassium carbonate 、 氢气 作用下， 以 四氢呋喃 为溶剂， 50.0 ℃ 、4.0 MPa 条件下， 反应 24.08h， 以78%的产率得到(E)-4-methyl-5-oxopent-3-enoic acid methyl ester
  参考文献：
  名称：

  串联定向区域选择性加氢甲酰化/β-消除：一种合成烯醛的实用方法

  摘要：

  报道了通过烯丙基 o-DPPB 酯的串联定向加氢甲酰化/β-消除工艺实际合成 α,β-不饱和醛。o-DPPB 基团作为加氢甲酰化对所需醛醇异构体的区域选择性的有效控制剂，随后被温和的标准碱原位消除。该反应对于制备 1,1-二取代和三取代烯醛是相当普遍的，并且与许多官能团相容。o-DPPBA 可以通过色谱法或以二乙基铵盐的形式沉淀来回收。

  DOI：

  10.1055/s-2008-1067140

文献信息

• Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways
  作者：Qi-Ying Hu、Gang Zhou、E. J. Corey

  DOI：10.1021/ja046154m

  日期：2004.10.1

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).
• KREBS, E. P.
  作者：KREBS, E. P.

  DOI：——

  日期：——
• Tandem-Directed Regioselective Hydroformylation/β-Elimination: A Practical Method for the Synthesis of Enals
  作者：Bernhard Breit、Achim Bruch、Antje Gebert

  DOI：10.1055/s-2008-1067140

  日期：2008.7

  A practical synthesis of α,β-unsaturated aldehydes by a tandem-directed hydroformylation/β -elimination process of allylic o-DPPB esters is reported. The o-DPPB group served as an effective controller for regioselectivity of the hydroformylation towards the desired aldolate isomer, and was subsequently eliminated in situ by mild standard bases. The reaction is rather general for the preparation of

  报道了通过烯丙基 o-DPPB 酯的串联定向加氢甲酰化/β-消除工艺实际合成 α,β-不饱和醛。o-DPPB 基团作为加氢甲酰化对所需醛醇异构体的区域选择性的有效控制剂，随后被温和的标准碱原位消除。该反应对于制备 1,1-二取代和三取代烯醛是相当普遍的，并且与许多官能团相容。o-DPPBA 可以通过色谱法或以二乙基铵盐的形式沉淀来回收。
• Enantioselective All-Carbon (4+2) Annulation by <i>N</i>-Heterocyclic Carbene Catalysis
  作者：Lisa Candish、Alison Levens、David W. Lupton

  DOI：10.1021/ja508542n

  日期：2014.10.15

  The enantioselective vinylogous Michael/aldol cascade is an underdeveloped approach to cyclohexenes. Herein we describe a highly enantioselective (most >= 98:2 er) and diastereoselective (all >= 15:1 dr) N-heterocyclic carbene catalyzed cycloisomerization of acyclic dienyl esters to cyclohexyl beta-lactones. Derivatizations avail cyclohexenes bearing four contiguous stereogenic centers, while mechanistic studies support olefin isomerization prior to cyclization.