N-methyl-3-phenyl-N-(2-(E)-phenylethenyl)-trans-oxiranecarboxamide

• 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: N-methyl-3-phenyl-N-(2-(E)-phenylethenyl)-trans-oxiranecarboxamide
• 英文别名: N-methyl-3-phenyl-N-(2-(E)-phenylethanyl)-trans-oxiranecarboxamide；(2R,3S)-N-methyl-3-phenyl-N-[(E)-2-phenylethenyl]oxirane-2-carboxamide
• 化学式: C₁₈H₁₇NO₂
• 分子量: 279.338
• InChiKey: SZEAIHVOVOPANP-AONBVXOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  32.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-methyl-3-phenyl-N-(2-(E)-phenylethenyl)-trans-oxiranecarboxamide 在 三氟乙酸 作用下， 以 叔丁醇 为溶剂， 反应 12.0h， 以72%的产率得到homoclausenamide
  参考文献：
  名称：

  Reversal of Nucleophilicity of Enamides in Water: Control of Cyclization Pathways by Reaction Media for the Orthogonal Synthesis of Dihydropyridinone and Pyrrolidinone Clausena Alkaloids

  摘要：

  A highly efficient, metal-free, and divergent method for the synthesis of 3,4-dihydropyridin-2-one and pyrrolidin-2-one Clausena alkaloids and their analogs is reported. While the oxirane-containing enamides underwent the TFA-mediated 6-endo-enamide-epoxide cyclization reaction in (BuOH)-O-t to produce homoclausenamides, an unprecedented nucleophilic reaction occurred at the alpha-carbon of enamides in water to yield 5-endo-enamide-epoxide cyclization products in excellent yields. The reversal of nucleophilicity of enamides in intramolecular cyclization is discussed in terms of steric and electronic effects of the oxirane-containing enamides.

  DOI：

  10.1021/ol800740h
• 作为产物：
  描述：

  別桂皮酸 在 叔丁基过氧化氢 、 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 N-methyl-3-phenyl-N-(2-(E)-phenylethenyl)-trans-oxiranecarboxamide
  参考文献：
  名称：

  通过有机金属加成到异氰酸酯上的不饱和酰胺：Lansamide-I，Lansiumamides AC和SB-204900的合成

  摘要：

  除异氰酸乙烯基酯外，还使用苯乙烯基格利雅（Styryl Grignard）制备天然存在的酰胺Lansamide-I，Laniumiumamides A和B，以及SB-204900；还报道了Laniumiumamide C的合成。

  DOI：

  10.1016/s0040-4039(00)00477-9

文献信息

• An elegant synthesis of Zetaclausenamide
  作者：Nianchun Ma、Kemei Wu、Liang Huang

  DOI：10.1016/j.ejmech.2007.05.010

  日期：2008.4

  Zetaclausenamide, which was isolated as a hepatoprotective agent from the leaves of medicinal plant Clausena lansium, was synthesized for the first time in six steps including Darzen's condensation, photoisomerization, and the final cyclization reactions.

  Zetaclausenamide是从药用植物Clausena lansium的叶子中分离出来的保肝剂，它是通过六个步骤（包括Darzen缩合，光异构化和最终环化反应）首次合成的。
• Highly efficient and concise synthesis of both antipodes of SB204900, clausenamide, neoclausenamide, homoclausenamide and ζ-clausenamide. Implication of biosynthetic pathways of clausena alkaloids
  作者：Luo Yang、De-Xian Wang、Qi-Yu Zheng、Jie Pan、Zhi-Tang Huang、Mei-Xiang Wang

  DOI：10.1039/b901965k

  日期：——

  The synthesis of both antipodes of N-methyl-N-[(Z)-styryl]-3-phenyloxirane-2-carboxamide (SB204900), clausenamide, neoclausenamide, homoclausenamide and ζ-clausenamide have been accomplished using (2S,3R)- and (2R,3S)-3-phenyloxirane-2-carboxamides as the starting materials, and SB204900 was found to be a common precursor to other N-heterocyclic clausena alkaloids. Mediated by Brønsted acids under different conditions, for example, SB204900 underwent efficient and diverse alkene-epoxide cyclization, enamide-epoxide cyclization and arene-epoxide cyclization reactions to produce the five-membered N-heterocyclic neoclausenamide, its 6-epimer, the six-membered N-heterocyclic homoclausenamide and the eight-membered N-heterocyclic ζ-clausenamide, respectively, in good to excellent yields. Regiospecific oxidation of neoclausenamide and its 6-epimer afforded neoclausenamidone. Enolization of neoclausenamidone in the presence of LiOH and the subsequent protonation under kinetic conditions at −78 °C led to the epimerization of neoclausenamidone into clausenamidone. Reduction of clausenamidone using NaBH4 furnished clausenamide in high yield.

  以(2S. 3R)-和(2R,3S)-3-苯基环氧乙烷-2-甲酰胺为起始原料，合成了 N-甲基-N-[(Z)-苯乙烯基]-3-苯基环氧乙烷-2-甲酰胺 (SB204900)、克劳森酰胺、新克劳森酰胺、同克劳森酰胺和 δ-克劳森酰胺的两个对位物、发现 SB204900 是其他 N-杂环克劳塞纳生物碱的常见前体。例如，在不同条件下由布氏酸介导，SB204900发生了高效、多样的烯-环氧化物环化反应、烯酰胺-环氧化物环化反应和炔-环氧化物环化反应，分别生成了五元N-杂环新氯森酰胺、其6-表聚体、六元N-杂环同氯森酰胺和八元N-杂环δ-氯森酰胺，收率从良好到极佳。新氯森酰胺及其 6-epimer 的 Regiospecific 氧化反应生成了新氯森酰胺酮。新氯硒脒酮在 LiOH 存在下发生烯醇化反应，随后在 °78 °C的动力学条件下发生质子化反应，从而使新氯硒脒酮发生表聚反应，生成克劳硒脒酮。用 NaBH4 还原克劳烯酰胺酮，可以得到高产率的克劳烯酰胺。
• Study of the intramolecular cyclization of N-methyl-3-phenyl-N-(2-(E)-phenylethenyl)-trans(cis)-oxiranecarboxamide – Syntheses of Homoclausenamide and Dehydroclausenamide
  作者：Nianchun Ma、Kemei Wu、Liang Huang

  DOI：10.1016/j.ejmech.2007.11.022

  日期：2008.8

  Homoclausenamide was synthesized for the first time, and the intramolecular cyclization study of N-methyl-3-phenyl-N-(2-(E)-phenylethenyl)-trans(cis)-oxiranecarboxamide well demonstrated how the stereochemistry affects the cyclization paths. (c) 2007 Elsevier Masson SAS. All rights reserved.
• Reversal of Nucleophilicity of Enamides in Water: Control of Cyclization Pathways by Reaction Media for the Orthogonal Synthesis of Dihydropyridinone and Pyrrolidinone <i>Clausena</i> Alkaloids
  作者：Luo Yang、Qi-Yu Zheng、De-Xian Wang、Zhi-Tang Huang、Mei-Xiang Wang

  DOI：10.1021/ol800740h

  日期：2008.6.1

  A highly efficient, metal-free, and divergent method for the synthesis of 3,4-dihydropyridin-2-one and pyrrolidin-2-one Clausena alkaloids and their analogs is reported. While the oxirane-containing enamides underwent the TFA-mediated 6-endo-enamide-epoxide cyclization reaction in (BuOH)-O-t to produce homoclausenamides, an unprecedented nucleophilic reaction occurred at the alpha-carbon of enamides in water to yield 5-endo-enamide-epoxide cyclization products in excellent yields. The reversal of nucleophilicity of enamides in intramolecular cyclization is discussed in terms of steric and electronic effects of the oxirane-containing enamides.
• Unsaturated enamides via organometallic addition to isocyanates: the synthesis of Lansamide-I, Lansiumamides A–C and SB-204900
  作者：Ian Stefanuti、Stephen A Smith、Richard J.K Taylor

  DOI：10.1016/s0040-4039(00)00477-9

  日期：2000.5

  Styryl Grignard addition to vinyl isocyanates is employed to prepare the naturally occurring enamides Lansamide-I, Lansiumamides A and B, and SB-204900; the synthesis of Lansiumamide C is also reported.

  除异氰酸乙烯基酯外，还使用苯乙烯基格利雅（Styryl Grignard）制备天然存在的酰胺Lansamide-I，Laniumiumamides A和B，以及SB-204900；还报道了Laniumiumamide C的合成。