benzyl (E)-2-oxo-4-phenylbut-3-enoate | 887642-11-7

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: benzyl (E)-2-oxo-4-phenylbut-3-enoate
• 英文别名: (E)-benzyl2-oxo-4-phenylbut-3-enoate
• CAS: 887642-11-7
• 化学式: C₁₇H₁₄O₃
• 分子量: 266.296
• InChiKey: FFWKYBGGQFHUOL-VAWYXSNFSA-N

物化性质

• 熔点：
  77-79 °C
• 沸点：
  422.0±38.0 °C(Predicted)
• 密度：
  1.184±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  benzyl (E)-2-oxo-4-phenylbut-3-enoate 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 (E)-5-benzyl 3-tert-butyl 4-(2-oxooxazolidine-3-carbonyl)-5-styryl-2-thioxooxazolidine-3,5-dicarboxylate
  参考文献：
  名称：

  手性N，N'-二氧化钇-三氟甲基磺酸盐配合物-α-异硫氰基酰亚胺催化α-酮基酯的不对称醛醇缩合环化反应

  摘要：

  AbstractA highly effective aldol cyclization of α‐isothiocyanato imide to both β,γ‐unsaturated α‐keto esters and aryl‐substituted α‐keto esters has been developed. A chiral N,N′‐dioxide–yttrium triflate complex was used as the catalyst. A series of cyclic thiocarbamates bearing chiral quaternary stereocenters was synthesized in good to high yields, excellent diastereo‐ (up to 25:1 dr) and enantioselectivities (up to 99 % ee). In addition, the reaction could be carried out on a gram‐scale, and other functionalized derivatives are also conveniently transformed. Interestingly, a discrepancy of diastereoselection was observed between the reactions of β,γ‐unsaturated α‐keto esters and aryl‐substituted α‐keto esters. Moreover, a substrate dependency of non‐linear effects was observed in this reaction. On the basis of the experimental results and the absolute configuration of the products, possible catalytic models have been proposed to explain the origin of the asymmetric process.magnified image

  DOI：

  10.1002/adsc.201300593
• 作为产物：
  描述：

  (E)-2-氧代-4-苯基-3-丁烯酸 在 草酰氯 、 potassium carbonate 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 13.33h， 生成 benzyl (E)-2-oxo-4-phenylbut-3-enoate
  参考文献：
  名称：

  β，γ-链烯基α-亚氨基酯的串联N-烷基化/同源Aldol反应

  摘要：

  该报告描述了β，γ-烯基α-亚氨基酯的高度区域选择性的串联N-烷基化/长春醛醇醛缩合反应。硫基团改善了定向乙烯基醇醛醇缩醛反应的区域选择性，提供了3-氨基-2-吡喃酮的新合成方法。

  DOI：

  10.1021/ol5007983

文献信息

• Highly Efficient Asymmetric Epoxidation of Electron-Deficient α,β-Enones and Related Applications to Organic Synthesis
  作者：Changwu Zheng、Yawen Li、Yingquan Yang、Haifeng Wang、Haifeng Cui、Junkang Zhang、Gang Zhao

  DOI：10.1002/adsc.200900041

  日期：2009.7

  The asymmetric epoxidation of electron‐deficient olefins has been achieved using inexpensive and readily available prolinols as catalysts with good to excellent yields and enantioselectivities. The utility of the resulting chiral epoxides was illustrated by elaboration to several synthetically useful compounds featuring a concise synthesis of (−)‐(5R,6S)‐balasubramide.

  使用价格低廉，易于获得的脯氨醇作为催化剂，可以实现电子不足的烯烃的不对称环氧化，其收率和对映选择性都非常好。详细阐述了几种合成有用的化合物，这些化合物以（-）-（5 R，6 S）-巴拉苏酰胺的简明合成为例，说明了所得手性环氧化物的实用性。
• Copper-Catalyzed Enantioselective Hetero-Diels–Alder Reaction of Danishefsky’s Diene with β,γ-Unsaturated α-Ketoesters
  作者：Yanbin Hu、Kun Xu、Sheng Zhang、Fengfeng Guo、Zhenggen Zha、Zhiyong Wang

  DOI：10.1021/ol5015009

  日期：2014.7.3

  A highly enantioselective hetero-Diels–Alder reaction of Danishefsky’s diene with β,γ-unsaturated α-ketoesters was developed for the first time by virtue of chiral copper complexes. This protocol provided a facile access to optically active dihydropyranones bearing a quaternary center with high enantioselectivities and good yields. Furthermore, on the basis of the isolated intermediate analysis, the

  借助手性铜配合物，首次开发了Danishefsky's二烯与β，γ-不饱和α-酮酸酯的高度对映选择性异Diels-Alder反应。该方案提供了容易获得的具有四元中心的旋光性二氢吡喃酮的对映选择性和高收率的方法。此外，基于分离的中间分析，反应途径是底物依赖性的。
• Highly Enantioselective Organocatalyzed Construction of Quaternary Carbon Centers via Cross-Aldol Reaction of Ketones in Water
  作者：Changwu Zheng、Yongyong Wu、Xiaosheng Wang、Gang Zhao

  DOI：10.1002/adsc.200800248

  日期：——

  The asymmetric construction of quaternary carbon centers via cross-aldol reactions of ketones with β,γ-unsaturated keto esters catalyzed by 4-(tert-butyldiphenylsilyloxy)-pyrrolidine-2-carboxylic acid in water is described. The adducts bearing two adjacent chiral centers were obtained in high yields, mostly up to 99% ee, and with high diastereoselectivities. The corresponding polyfunctional products

  季碳中心的非对称结构通过与β酮的交叉醛醇缩合反应，γ不饱和酮酯由4-（催化叔-butyldiphenylsilyloxy） -吡咯烷-2-羧酸在水中的酸进行说明。带有两个相邻手性中心的加合物以高收率获得，大多数是高达99％ee，并且具有非对映选择性。相应的多官能产物也可以容易地转化为具有三个手性中心的有用的内酯。
• [EN] PROCESS FOR PRODUCING CARBOXYLIC ACID ESTER<br/>[FR] PROCÉDÉ DE PRODUCTION D'UN ESTER D'ACIDE CARBOXYLIQUE
  申请人：SUMITOMO CHEMICAL CO

  公开号：WO2012176930A1

  公开（公告）日：2012-12-27

  An object of the present invention is to provide a new process which can produce a carboxylic acid ester from an aldehyde. The object is achieved by a process for producing a carboxylic acid ester, including the step of mixing a compound represented by the formula (2-1): (wherein R2 represents an alkyl group optionally having a substituent, or the like; R3 and R4 each represent independently an alkyl group optionally having a substituent, or the like, or R3 and R4 are taken together to form a divalent hydrocarbon group optionally having a substituent, or the like; Y represents a group represented by -S- or a group represented by -N(R5)-; R5 represents an alkyl group optionally having a substituent, or the like, or R5 is taken together with R4 to form a divalent hydrocarbon group optionally having a substituent; and X- represents an anion), a base, an alcohol, oxygen and an aldehyde to oxidize the aldehyde.

  本发明的一个目的是提供一种新的过程，可以从醛中产生羧酸酯。该目的通过一种生产羧酸酯的过程实现，包括混合以下公式表示的化合物（2-1）的步骤：（其中R2代表一个烷基基团，可选地具有取代基，或类似物；R3和R4分别独立地代表一个烷基基团，可选地具有取代基，或类似物，或者R3和R4结合在一起形成一个二价碳氢基团，可选地具有取代基，或类似物；Y代表一个由-S-表示的基团或由-N(R5)-表示的基团；R5代表一个烷基基团，可选地具有取代基，或类似物，或R5与R4结合在一起形成一个二价碳氢基团，可选地具有取代基；X-代表一个阴离子），一种碱，一种醇，氧气和一种醛来氧化该醛。
• [EN] PROCESS FOR PRODUCING CARBOXYLIC ACID ESTER<br/>[FR] PROCÉDÉ DE PRODUCTION D'ESTER D'ACIDE CARBOXYLIQUE
  申请人：SUMITOMO CHEMICAL CO

  公开号：WO2012026617A1

  公开（公告）日：2012-03-01

  The present invention relates to a process for producing a carboxylic acid ester, comprising a step of oxidizing an aldehyde by mixing an alcohol, carbon dioxide, the aldehyde and at least one compound selected from the group consisting of compounds represented by the formulae (2-1) and (2-2): wherein R2 represents an alkyl group optionally having a substituent or the like; R3 and R4 each independently represents an alkyl group optionally having a substituent or the like or R3 and R4 are linked together to form a divalent hydrocarbon group optionally having a substituent or the like; Y represents a group of -S- or a group of -N(R5)-, wherein R5 represents an alkyl group optionally having a substituent or the like, or R5 is linked to R4 to form a divalent hydrocarbon group optionally having a substituent; and R8 represents an alkyl group.

  本发明涉及一种生产羧酸酯的方法，包括通过混合醇、二氧化碳、醛和来自由式（2-1）和（2-2）所代表的化合物组成的群体中至少选取一种化合物，氧化醛的步骤：其中R2代表可能具有取代基等的烷基基团；R3和R4各自独立地代表可能具有取代基等的烷基基团，或者R3和R4连接在一起形成可能具有取代基等的二价碳氢基团；Y代表一个-S-基团或一个-N(R5)-基团，其中R5代表可能具有取代基等的烷基基团，或者R5连接到R4形成可能具有取代基的二价碳氢基团；R8代表一个烷基基团。