benzyl 3-acetoxy-2-vinylidenepentanoate | 1257228-77-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzyl 3-acetoxy-2-vinylidenepentanoate
• CAS: 1257228-77-5
• 化学式: C₁₆H₁₈O₄
• 分子量: 274.317
• InChiKey: YLSUJQZMFTVFGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl 3-acetoxy-2-vinylidenepentanoate 、 苯甲酰乙腈 在 三乙烯二胺 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以53%的产率得到benzyl 5-cyano-4-ethyl-2-methyl-6-phenyl-4H-pyran-3-carboxylate
  参考文献：
  名称：

  Amine-catalyzed (3+n) annulations of 2-(acetoxymethyl)buta-2,3-dienoates with 1,n-bisnucleophiles (n = 3–5)

  摘要：

  已经开发出一种以三级胺催化的正式 (3+n) 环化反应，将 2-(乙酰氧基甲基)丁-2,3-二烯酸酯与 1,n-双亲核试剂进行反应，提供了一种简单的合成杂环化合物的方法。机制涉及串联的 SN2'–SN2' 取代反应和迈克尔加成反应，已经明确。

  DOI：

  10.1039/c0cc01966f
• 作为产物：
  描述：

  在 吡啶 、 sodium iodide 、 tin(ll) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 7.0h， 生成 benzyl 3-acetoxy-2-vinylidenepentanoate
  参考文献：
  名称：

  Amine-Catalyzed Asymmetric (3 + 3) Annulations of β′-Acetoxy Allenoates: Enantioselective Synthesis of 4H-Pyrans

  摘要：

  The asymmetric (3 + 3) annulations of beta'-acetoxy allenoates with either 3-oxo-nitriles or pyrazolones have been realized by using 6'-deoxy-6'-[(L)-N,N-(2,2'-oxidiethyl)-valine amido]quinine (6h) as the catalyst. The three functions of catalyst 6h, including Lewis base (quinuclidine N), H-bond donor (amide NH), and Bronsted base (morpholine N), cooperatively take crucial roles on the chemo- and enantioselectivity, allowing for the construction of 4H-pyran and 4H-pyrano[2,3-c]pyrazole in high yields and enantioselectivity.

  DOI：

  10.1021/jacs.6b04935

文献信息

• Biphenyl-Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes
  作者：Daniel T. Ziegler、Lorena Riesgo、Takuya Ikeda、Yuji Fujiwara、Gregory C. Fu

  DOI：10.1002/anie.201405854

  日期：2014.11.24

  fully substituted stereocenter [either all‐carbon or heteroatom‐substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four‐carbon coupling partner is not the turnover‐limiting step of the catalytic cycle.

  由于环戊烷亚基在生物活性化合物中频繁出现，开发有效的催化不对称合成方法是一个重要目标。本文介绍了一个新的手性亲核催化剂家族，联苯衍生的膦，我们将它们应用于有用的 [4+1] 环化的对映选择性变体。可以使用一系列单碳偶联伙伴，从而产生带有完全取代立体中心的环戊烯 [全碳或杂原子取代（硫和磷）]。环戊烷环其他四个位置的立体中心也可以以良好的立体选择性引入。
• Access to thiopyrano[2,3-b]indole via tertiary amine-catalyzed formal (3+3) annulations of β′-acetoxy allenoates with indoline-2-thiones
  作者：Chunjie Ni、Yuwen Zhang、Yading Hou、Xiaofeng Tong

  DOI：10.1039/c6cc09788j

  日期：——

  The DABCO-catalyzed formal (3+3) annulations of [small beta]'-acetoxy allenoates with indoline-2-thiones are described, which provide a facile access to thiopyrano[2,3-b]indole under mild reaction conditions. The reaction might proceed SN2'-SN2' type process...

  描述了DABCO催化的吲哚啉-2-硫酮的小β'-乙酰氧基脲酸酯的正式（3 + 3）环化反应，可在温和的反应条件下轻松获得噻喃并[2,3-b]吲哚。反应可能会继续进行SN2'-SN2'类型的过程...
• Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β′-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine
  作者：Yiting Gu、Pengfei Hu、Chunjie Ni、Xiaofeng Tong

  DOI：10.1021/jacs.5b03273

  日期：2015.5.20

  Two classes of phosphine-catalyzed addition/cycloaddition domino reactions of beta'-acetoxy allenoate 1 have been developed. The reaction of 1 with 2-acyl-3-methyl-acrylonitrile 2 readily occurs to give 2-oxabicyclo[3.3.1]nonane 3, furnishing the beta'-addition/[4 + 4] cycloaddition domino sequence. In this sequence, beta'C of allenoate 1 is an electrophilic center, and its beta'C and gamma C serve as a 1,4-dipole. When the other reaction partner is switched to 2-acyl-3-(2-pyrrole)-acrylonitrile 8, a gamma-addition/[3 + 2] cycloaddition domino reaction is instead observed, in which allenoate 1 exhibits dual electrophilic reactivity of gamma C and 1,3-dipole chemical behavior of beta C and beta'C. Furthermore, both of these two asymmetric variants have also been achieved with up to 93% ee. The domino reactions presented in this report are valuable for highly stereoselective construction of complex structures under mild reaction conditions.
• Amine-Catalyzed Asymmetric (3 + 3) Annulations of β′-Acetoxy Allenoates: Enantioselective Synthesis of 4<i>H</i>-Pyrans
  作者：Chunjie Ni、Xiaofeng Tong

  DOI：10.1021/jacs.6b04935

  日期：2016.6.29

  The asymmetric (3 + 3) annulations of beta'-acetoxy allenoates with either 3-oxo-nitriles or pyrazolones have been realized by using 6'-deoxy-6'-[(L)-N,N-(2,2'-oxidiethyl)-valine amido]quinine (6h) as the catalyst. The three functions of catalyst 6h, including Lewis base (quinuclidine N), H-bond donor (amide NH), and Bronsted base (morpholine N), cooperatively take crucial roles on the chemo- and enantioselectivity, allowing for the construction of 4H-pyran and 4H-pyrano[2,3-c]pyrazole in high yields and enantioselectivity.
• Amine-catalyzed (3+n) annulations of 2-(acetoxymethyl)buta-2,3-dienoates with 1,n-bisnucleophiles (n = 3–5)
  作者：Chaolong Li、Qiongmei Zhang、Xiaofeng Tong

  DOI：10.1039/c0cc01966f

  日期：——

  A tertiary amine-catalyzed formal (3+n) annulation of 2-(acetoxymethyl)buta-2,3-dienoate with 1,n-binucleophiles has been developed, which provides a facile entry to heterocyclic compounds. The mechanism, involving tandem SN2′–SN2′ substitution and Michael addition, has also been established.

  已经开发出一种以三级胺催化的正式 (3+n) 环化反应，将 2-(乙酰氧基甲基)丁-2,3-二烯酸酯与 1,n-双亲核试剂进行反应，提供了一种简单的合成杂环化合物的方法。机制涉及串联的 SN2'–SN2' 取代反应和迈克尔加成反应，已经明确。