ethyl (2E,4E,6S)-6-[[(E)-4-ethoxy-4-oxobut-2-enyl]amino]-7-methylocta-2,4-dienoate | 244034-00-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (2E,4E,6S)-6-[[(E)-4-ethoxy-4-oxobut-2-enyl]amino]-7-methylocta-2,4-dienoate
• CAS: 244034-00-2
• 化学式: C₁₇H₂₇NO₄
• 分子量: 309.406
• InChiKey: KLPOOQNYBKOLRE-BAIDLZMKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  22
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (2E,4E,6S)-6-[[(E)-4-ethoxy-4-oxobut-2-enyl]amino]-7-methylocta-2,4-dienoate 在 三乙胺 作用下， 以 四氢呋喃 、 氘代氯仿 为溶剂， 反应 40.5h， 生成 (1S,3aS,4R,5S,7aR)-2-Benzoyl-1-isopropyl-2,3,3a,4,5,7a-hexahydro-1H-isoindole-4,5-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Diels−Alder Reactions of Amino Acid-Derived Trienes

  摘要：

  Triene precursors (1a-e, 2a-k) were constructed for substrate-controlled asymmetric Diels-Alder reactions. Boc-L-phenylalanal and Boc-L-valinal were condensed with triethyl phosphonoacetate or 2-phosphonopropionate to generate the alpha,beta-unsaturated esters as dienophiles. Removal of the Boc group to give free amines 4a-d, which after, or without N-benzylation, were treated with 3,5-hexadienoyl chloride to give 1a-e, or with 2,4-hexadienoyl chloride to afford 2a-f. The trienes 2g-i were prepared via reductive alkylation of amines 4a-i with 2,4-hexadienal. The secondary amide triene la failed to yield any Diels-Alder product when heated at 170 degrees C. The tertiary amide trienes 1b-e produced in refluxing toluene the major cycloaddition products that were cia-fused and derived from the exo transition states. Trienes 2a-k underwent surprisingly facile Diels-Alder reactions to produce the major trans-fused isomers that Were derived from the endo transition states. For trienes 2b-h and 2j,k, Diels-Alder reactions proceeded at room temperature. For the primary amide 2a, the Diels-Alder reaction proceeded smoothly in refluxing toluene. The tertiary amide triene 22 was constructed to have two electron-withdrawing ester substituents at the termini of the triene. The Diels-Alder reaction of 22 took place spontaneously at room temperature upon benzoylation of the secondary amine 21 and produced a single isomer derived from the endo transition state. 1,3-Allylic strain is discussed as an important factor in control of the diastereoselectivity.

  DOI：

  10.1021/jo990459f
• 作为产物：
  描述：

  4-溴巴豆酸乙酯 、 [(3S,4E,6E)-8-ethoxy-2-methyl-8-oxoocta-4,6-dien-3-yl]azanium;2,2,2-trifluoroacetate 在 4-二甲氨基吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 40.0h， 以52%的产率得到ethyl (2E,4E,6S)-6-[[(E)-4-ethoxy-4-oxobut-2-enyl]amino]-7-methylocta-2,4-dienoate
  参考文献：
  名称：

  Diels−Alder Reactions of Amino Acid-Derived Trienes

  摘要：

  Triene precursors (1a-e, 2a-k) were constructed for substrate-controlled asymmetric Diels-Alder reactions. Boc-L-phenylalanal and Boc-L-valinal were condensed with triethyl phosphonoacetate or 2-phosphonopropionate to generate the alpha,beta-unsaturated esters as dienophiles. Removal of the Boc group to give free amines 4a-d, which after, or without N-benzylation, were treated with 3,5-hexadienoyl chloride to give 1a-e, or with 2,4-hexadienoyl chloride to afford 2a-f. The trienes 2g-i were prepared via reductive alkylation of amines 4a-i with 2,4-hexadienal. The secondary amide triene la failed to yield any Diels-Alder product when heated at 170 degrees C. The tertiary amide trienes 1b-e produced in refluxing toluene the major cycloaddition products that were cia-fused and derived from the exo transition states. Trienes 2a-k underwent surprisingly facile Diels-Alder reactions to produce the major trans-fused isomers that Were derived from the endo transition states. For trienes 2b-h and 2j,k, Diels-Alder reactions proceeded at room temperature. For the primary amide 2a, the Diels-Alder reaction proceeded smoothly in refluxing toluene. The tertiary amide triene 22 was constructed to have two electron-withdrawing ester substituents at the termini of the triene. The Diels-Alder reaction of 22 took place spontaneously at room temperature upon benzoylation of the secondary amine 21 and produced a single isomer derived from the endo transition state. 1,3-Allylic strain is discussed as an important factor in control of the diastereoselectivity.

  DOI：

  10.1021/jo990459f

文献信息

• Diels−Alder Reactions of Amino Acid-Derived Trienes
  作者：William V. Murray、Sengen Sun、Ignatius J. Turchi、Frank K. Brown、A. Diane Gauthier

  DOI：10.1021/jo990459f

  日期：1999.8.1

  Triene precursors (1a-e, 2a-k) were constructed for substrate-controlled asymmetric Diels-Alder reactions. Boc-L-phenylalanal and Boc-L-valinal were condensed with triethyl phosphonoacetate or 2-phosphonopropionate to generate the alpha,beta-unsaturated esters as dienophiles. Removal of the Boc group to give free amines 4a-d, which after, or without N-benzylation, were treated with 3,5-hexadienoyl chloride to give 1a-e, or with 2,4-hexadienoyl chloride to afford 2a-f. The trienes 2g-i were prepared via reductive alkylation of amines 4a-i with 2,4-hexadienal. The secondary amide triene la failed to yield any Diels-Alder product when heated at 170 degrees C. The tertiary amide trienes 1b-e produced in refluxing toluene the major cycloaddition products that were cia-fused and derived from the exo transition states. Trienes 2a-k underwent surprisingly facile Diels-Alder reactions to produce the major trans-fused isomers that Were derived from the endo transition states. For trienes 2b-h and 2j,k, Diels-Alder reactions proceeded at room temperature. For the primary amide 2a, the Diels-Alder reaction proceeded smoothly in refluxing toluene. The tertiary amide triene 22 was constructed to have two electron-withdrawing ester substituents at the termini of the triene. The Diels-Alder reaction of 22 took place spontaneously at room temperature upon benzoylation of the secondary amine 21 and produced a single isomer derived from the endo transition state. 1,3-Allylic strain is discussed as an important factor in control of the diastereoselectivity.