cis-α-Phenylcinnamic acid dimethylamide | 25341-20-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: cis-α-Phenylcinnamic acid dimethylamide
• 英文别名: (Z)-N,N-dimethyl-2,3-diphenylacrylamide；(Z)-N,N-dimethyl-2,3-dipheyl-2-propenamide；(Z)-N,N-dimethyl-2,3-diphenylprop-2-enamide
• CAS: 25341-20-2
• 化学式: C₁₇H₁₇NO
• 分子量: 251.328
• InChiKey: LZMHYSJPEMLTPD-SSZFMOIBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-二甲基乙酰胺 、 cis-α-Phenylcinnamic acid dimethylamide 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 (2S,3S)-2,3-Diphenyl-pentanedioic acid bis-dimethylamide 、 (2S,3R)-2,3-Diphenyl-pentanedioic acid bis-dimethylamide
  参考文献：
  名称：

  Kinetic asymmetric protonation as a stereochemistry determining step in theMichael addition of acetic acid derivatives to ?-substituted cinnamic acid derivatives

  摘要：

  The reaction between acetic acid derivatives and alpha-substituted cinnamic acid derivatives has been studied in THF and THF:HMPT (80:20) as an alternative pathway of the Michael addition of phenylacetic and cinnamic acid derivatives. The regioselectivity observed is found to depend on the acceptor functional group and its geometry but not on the solvent used. The diastereoselectivity of the conjugate addition results from kinetic protonation of diastereotopic enolates (1,2-asymmetric induction). It varies from low in the presence of HMPT to considerable or even high in pure THF. The favoured anti or syn configuration in THF depends on the nature of the enolate. The results obtained are rationalized in terms of protonation via transition structures different in type (open us. chelated) and geometry.

  DOI：

  10.1007/bf00811020
• 作为产物：
  描述：

  2-氯乙炔基苯 在 三氟化硼乙醚 、 碘 作用下， 以 乙醚 、 硝基苯 为溶剂， 生成 cis-α-Phenylcinnamic acid dimethylamide
  参考文献：
  名称：

  Fuks,R.; Viehe,H.G., Chemische Berichte, 1970, vol. 103, p. 564 - 572

  摘要：

  DOI：

文献信息

• Cobalt/Lewis Acid Catalysis for Hydrocarbofunctionalization of Alkynes via Cooperative C–H Activation
  作者：Chang-Sheng Wang、Sabrina Di Monaco、Anh Ngoc Thai、Md. Shafiqur Rahman、Benjamin Piaoxiang Pang、Chen Wang、Naohiko Yoshikai

  DOI：10.1021/jacs.0c06412

  日期：2020.7.22

  also display distinct site-selectivity toward C-H activation of pyridone and pyridine derivatives. In particular, a completely C4-selective alkenylation of pyridine has been achieved for the first time. Meanwhile, the present catalytic system proved to promote exclusively C5-selective alkenylation of imidazo[1,2-a]pyridine derivatives. Mechanistic studies including DFT calculations on the Co/Al-catalyzed

  已发现由钴-二膦配合物和路易斯酸 (LA)（如 AlMe3）组成的催化体系可促进炔烃与路易斯碱性和缺电子底物（如甲酰胺、吡啶酮、吡啶和相关嗪、咪唑 [ 1,2-a] 吡啶和唑衍生物通过位点选择性 CH 活化。与已知的用于类似转化的 Ni/LA 催化系统相比，本催化系统不仅具有使用廉价且实验室稳定的预催化剂和配体如 Co(acac)3 和 1,3-双(二苯基膦)丙烷 (dppp) 的方便设置的特点。 )，但也对吡啶酮和吡啶衍生物的 CH 活化显示出不同的位点选择性。特别是，首次实现了吡啶的完全 C4 选择性烯基化。同时，本催化系统证明仅促进咪唑并 [1,2-a] 吡啶衍生物的 C5 选择性烯基化。包括 Co/Al 催化将甲酰胺加成到炔烃的 DFT 计算在内的机理研究表明，该反应涉及氨基甲酰基 CH 键的裂解作为限速步骤，该反应通过配体到配体的氢转移 (LLHT) 进行导致烯基（氨基甲酰基）钴中间体的机制。
• Nakao, Yoshiaki; Idei, Hiroaki; Kanyiva, Kyalo Stephen, Journal of the American Chemical Society, 2009, vol. 131, p. 5070 - 5071
  作者：Nakao, Yoshiaki、Idei, Hiroaki、Kanyiva, Kyalo Stephen、Hiyama, Tamejiro

  DOI：——

  日期：——
• Fuks,R.; Viehe,H.G., Chemische Berichte, 1970, vol. 103, p. 564 - 572
  作者：Fuks,R.、Viehe,H.G.

  DOI：——

  日期：——
• Kinetic asymmetric protonation as a stereochemistry determining step in theMichael addition of acetic acid derivatives to ?-substituted cinnamic acid derivatives
  作者：L. Viteva、L. Gorrichon

  DOI：10.1007/bf00811020

  日期：——

  The reaction between acetic acid derivatives and alpha-substituted cinnamic acid derivatives has been studied in THF and THF:HMPT (80:20) as an alternative pathway of the Michael addition of phenylacetic and cinnamic acid derivatives. The regioselectivity observed is found to depend on the acceptor functional group and its geometry but not on the solvent used. The diastereoselectivity of the conjugate addition results from kinetic protonation of diastereotopic enolates (1,2-asymmetric induction). It varies from low in the presence of HMPT to considerable or even high in pure THF. The favoured anti or syn configuration in THF depends on the nature of the enolate. The results obtained are rationalized in terms of protonation via transition structures different in type (open us. chelated) and geometry.