Methyl (E)-5-(phenylamino)-5-(2-pyridyl)-2-pentenoate

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Methyl (E)-5-(phenylamino)-5-(2-pyridyl)-2-pentenoate
• 英文别名: methyl (E)-5-anilino-5-pyridin-2-ylpent-2-enoate
• 化学式: C₁₇H₁₈N₂O₂
• 分子量: 282.342
• InChiKey: LXSQSMJIKBUGKL-KPKJPENVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  51.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (E)-N-Phenyl-1-(2-pyridinyl)methanimine 、 3-丁烯酸甲酯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以99%的产率得到Methyl (E)-5-(phenylamino)-5-(2-pyridyl)-2-pentenoate
  参考文献：
  名称：

  Dualistic Reactivity of Lithium and Zinc Dienolates with Imines: Effects of Counterion, Temperature, and Substituents on .alpha.- and .gamma.-Coupling

  摘要：

  Lithium and zinc dienolates of 3-butenoic, 3-methyl-2-butenoic, 3-pentenoic, and 4-phenyl-3-butenoic methyl esters are reacted with imines R(1)C(H)=NR(2)[3a: R(1) = 2-pyridyl, R(2) = Ph; 3b: R(1) = Me(3)-SiC=C; R(2) = Ph; 3c: R(1) = 2-pyridyl, R(2) = (R)-PhCK(CH3); 3d: R(1) = Me(3)SiC=C; R(2) = (R)-PhCH(CH3)]. Depending on metal counterion, temperature, and substituents, the C-C coupling occurs either at the 2-position (alpha-coupling) or at the C-position (gamma-coupling) of the dienolate, giving beta-amino esters and alpha,beta-unsaturated esters, respectively. The alpha-coupling occurs at -78 degrees C and is reversible, whereas gamma-coupling products are formed upon warming to -20 degrees C. The C-C coupled products may undergo irreversible ring closure to beta-lactams (from beta-amino esters) or 5,6-dihydropyridin-2-ones (from Z)-alpha,beta-unsaturated esters). Starting from enantiomerically pure imine 3c, high (71-92%) asymmetric inductions were realized in both beta-lactams and 5,6-dihydropyridin-2-ones; gamma-coupling of enolate 2a and chiral imine 3d occurred with low diastereoselectivity (15%). Four factors favor the formation of beta-lactams: (i) the use of zinc dienolates, (ii) 4-substitution of the dienolates, (iii) nonaromatic imine N-substituents, and (iv) a low reaction temperature (-78 degrees C). The product formation is discussed in terms of six-membered cyclic transition states, involving either zinc enolates (alpha-coupling) or isomeric allylzinc species (gamma-coupling).

  DOI：

  10.1021/jo00104a048

文献信息

• Dualistic Reactivity of Lithium and Zinc Dienolates with Imines: Effects of Counterion, Temperature, and Substituents on .alpha.- and .gamma.-Coupling
  作者：Hendrik L. van Maanen、Henk Kleijn、Johann T. B. H. Jastrzebski、Miles T. Lakin、Anthony L. Spek、Gerard van Koten

  DOI：10.1021/jo00104a048

  日期：1994.12

  Lithium and zinc dienolates of 3-butenoic, 3-methyl-2-butenoic, 3-pentenoic, and 4-phenyl-3-butenoic methyl esters are reacted with imines R(1)C(H)=NR(2)[3a: R(1) = 2-pyridyl, R(2) = Ph; 3b: R(1) = Me(3)-SiC=C; R(2) = Ph; 3c: R(1) = 2-pyridyl, R(2) = (R)-PhCK(CH3); 3d: R(1) = Me(3)SiC=C; R(2) = (R)-PhCH(CH3)]. Depending on metal counterion, temperature, and substituents, the C-C coupling occurs either at the 2-position (alpha-coupling) or at the C-position (gamma-coupling) of the dienolate, giving beta-amino esters and alpha,beta-unsaturated esters, respectively. The alpha-coupling occurs at -78 degrees C and is reversible, whereas gamma-coupling products are formed upon warming to -20 degrees C. The C-C coupled products may undergo irreversible ring closure to beta-lactams (from beta-amino esters) or 5,6-dihydropyridin-2-ones (from Z)-alpha,beta-unsaturated esters). Starting from enantiomerically pure imine 3c, high (71-92%) asymmetric inductions were realized in both beta-lactams and 5,6-dihydropyridin-2-ones; gamma-coupling of enolate 2a and chiral imine 3d occurred with low diastereoselectivity (15%). Four factors favor the formation of beta-lactams: (i) the use of zinc dienolates, (ii) 4-substitution of the dienolates, (iii) nonaromatic imine N-substituents, and (iv) a low reaction temperature (-78 degrees C). The product formation is discussed in terms of six-membered cyclic transition states, involving either zinc enolates (alpha-coupling) or isomeric allylzinc species (gamma-coupling).