allyl 2-cyano-2-phenylacetate

• 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: allyl 2-cyano-2-phenylacetate
• 英文别名: Prop-2-enyl 2-cyano-2-phenylacetate
• 化学式: C₁₂H₁₁NO₂
• 分子量: 201.225
• InChiKey: DFBTYPGEVWDCMT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  溴甲烷 、 allyl 2-cyano-2-phenylacetate 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 allyl 2-cyano-2-phenylpropanoate
  参考文献：
  名称：

  Regiospecific Decarboxylative Allylation of Nitriles

  摘要：

  Palladium-catalyzed decarboxylative alpha-allylation of nitriles readily occurs with use of Pd-2(dba)(3) and rac-BINAP. This catalyst mixture also allows the highly regiospecific alpha-allylation of nitrites in the presence of much more acidic (x-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement.

  DOI：

  10.1021/ol902065p
• 作为产物：
  描述：

  2-氰基-2-苯乙酸 、 烯丙醇 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 生成 allyl 2-cyano-2-phenylacetate
  参考文献：
  名称：

  Regiospecific Decarboxylative Allylation of Nitriles

  摘要：

  Palladium-catalyzed decarboxylative alpha-allylation of nitriles readily occurs with use of Pd-2(dba)(3) and rac-BINAP. This catalyst mixture also allows the highly regiospecific alpha-allylation of nitrites in the presence of much more acidic (x-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement.

  DOI：

  10.1021/ol902065p

文献信息

• Regioselective Asymmetric Allylic Alkylation Reaction of<b>α</b>-Cyanoacet­ates Catalyzed by a Heterobimetallic Platina-/Palladacycle
  作者：Marcel Weiss、Julia Holz、René Peters

  DOI：10.1002/ejoc.201501290

  日期：2016.1

  describe the use of heterobimetallic PtII/PdII complexes, which probably activate the olefinic substrates through an SN2′ pathway. The reaction of α-cyanoacetates delivers linear allylation products with exclusive regioselectivity and high E/Z-selectivity for the new C=C double bond. Although the enantioselectivities attained are moderate, they are significantly higher than with related mono-PdII or -PtII

  烯丙基取代反应为 CH 酸性亲核试剂的功能化提供了有价值的工具。通常，控制亲核反应物产生的立体中心仍然是一个挑战。解决这个问题的大多数研究采用具有低金属氧化态（例如 Pd0）的金属配合物通过氧化加成形成烯丙基配合物。在这篇文章中，我们描述了异双金属 PtII/PdII 复合物的使用，它可能通过 SN2' 途径激活烯烃底物。α-氰基乙酸酯的反应产生线性烯丙基化产物，对新的 C=C 双键具有独特的区域选择性和高 E/Z 选择性。尽管获得的对映选择性适中，但它们明显高于相关的单 PdII 或 -PtII 催化剂或相应的双 PdII 复合物，这表明不同金属的合作。对照实验表明同时激活两个反应伙伴。
• US4024123A
  申请人：——

  公开号：US4024123A

  公开（公告）日：1977-05-17
• US4607098A
  申请人：——

  公开号：US4607098A

  公开（公告）日：1986-08-19
• US4757135A
  申请人：——

  公开号：US4757135A

  公开（公告）日：1988-07-12
• Regiospecific Decarboxylative Allylation of Nitriles
  作者：Antonio Recio、Jon A. Tunge

  DOI：10.1021/ol902065p

  日期：2009.12.17

  Palladium-catalyzed decarboxylative alpha-allylation of nitriles readily occurs with use of Pd-2(dba)(3) and rac-BINAP. This catalyst mixture also allows the highly regiospecific alpha-allylation of nitrites in the presence of much more acidic (x-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement.