(6S)-6-N-tert-butoxycarbonylamino-7-methyl-trans,trans-2,4-octadienoic acid, ethyl ester | 244033-74-7

• 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: (6S)-6-N-tert-butoxycarbonylamino-7-methyl-trans,trans-2,4-octadienoic acid, ethyl ester
• 英文别名: ethyl (2E,4E,6S)-7-methyl-6-[(2-methylpropan-2-yl)oxycarbonylamino]octa-2,4-dienoate
• CAS: 244033-74-7
• 化学式: C₁₆H₂₇NO₄
• 分子量: 297.395
• InChiKey: KVVBGRYSKDZVTR-GQQKUERGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (6S)-6-N-tert-butoxycarbonylamino-7-methyl-trans,trans-2,4-octadienoic acid, ethyl ester 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 生成 (6S)-6-N-benzylamino-7-methyl-trans,trans-2,4-octadienoic acid, ethyl 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：

  ethyl (S,E)-4-((tert-butoxycarbonyl)amino)-5-methylhex-2-enoate 在 三氟化硼乙醚 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 11.5h， 生成 (6S)-6-N-tert-butoxycarbonylamino-7-methyl-trans,trans-2,4-octadienoic acid, ethyl ester
  参考文献：
  名称：

  主链延伸的π-共轭氨基酯的立体选择性合成

  摘要：

  利用 Wittig 反应合成共轭多重双键的情况很少见。我们检查了 Wittig 反应在 N-保护的氨基酸主链上构建共轭二和三碳碳双键的效用。主链中具有多个碳-碳双键的N -Boc 氨基酸的乙酯以优异的产率分离，具有出色的双键E-选择性。以DIBAL-H和BF 3 ·OEt 2为原料选择性地合成了α,β-不饱和γ-氨基酯的烯丙醇。使用 IBX 氧化将烯丙醇转化为醛。使用此协议，我们合成了N -Boc-( E , E)-α,β,γ,δ-不饱和ε-氨基酸，具有各种侧链官能团和N -Boc-( E , E , E )-α,β,γ,δ,ε,ζ-不饱和乙酯产量高的 η-氨基酸。我们推测异常的E选择性可能是由于 Wittig 反应的平面过渡态与双键 p 轨道的稳定。在氨基酸的合成中没有观察到外消旋化。报道的过程可以作为合成多个共轭碳-碳双键的极好途径。

  DOI：

  10.1039/d3ob00090g

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.
• Stereoselective synthesis of backbone extended π-conjugated amino esters
  作者：Sachin A. Nalawade、Manjeet Singh、DRGKoppalu R. Puneeth Kumar、Sanjit Dey、Hosahudya N. Gopi

  DOI：10.1039/d3ob00090g

  日期：——

  alcohols were transformed into aldehydes using IBX oxidation. Using this protocol, we synthesized ethyl esters of N-Boc-(E,E)-α,β,γ,δ-unsaturated ε-amino acids with various side-chain functionalities and ethyl esters of N-Boc-(E,E,E)-α,β,γ,δ,ε,ζ-unsaturated η-amino acids with excellent yields. We speculated the exceptional E-selectivity is probably due to the stabilization of the planar transition state

  利用 Wittig 反应合成共轭多重双键的情况很少见。我们检查了 Wittig 反应在 N-保护的氨基酸主链上构建共轭二和三碳碳双键的效用。主链中具有多个碳-碳双键的N -Boc 氨基酸的乙酯以优异的产率分离，具有出色的双键E-选择性。以DIBAL-H和BF 3 ·OEt 2为原料选择性地合成了α,β-不饱和γ-氨基酯的烯丙醇。使用 IBX 氧化将烯丙醇转化为醛。使用此协议，我们合成了N -Boc-( E , E)-α,β,γ,δ-不饱和ε-氨基酸，具有各种侧链官能团和N -Boc-( E , E , E )-α,β,γ,δ,ε,ζ-不饱和乙酯产量高的 η-氨基酸。我们推测异常的E选择性可能是由于 Wittig 反应的平面过渡态与双键 p 轨道的稳定。在氨基酸的合成中没有观察到外消旋化。报道的过程可以作为合成多个共轭碳-碳双键的极好途径。