Ethyl (2E,4S,5R,6E)-5-Methoxy-2,4-dimethyl-7-phenyl-2,6-heptadienoate | 138694-20-9

• 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: Ethyl (2E,4S,5R,6E)-5-Methoxy-2,4-dimethyl-7-phenyl-2,6-heptadienoate
• 英文别名: ethyl (2E,4S,5S,6E)-5-methoxy-2,4-dimethyl-7-phenylhepta-2,6-dienoate
• CAS: 138694-20-9
• 化学式: C₁₈H₂₄O₃
• 分子量: 288.387
• InChiKey: CVOIARACJLFILS-WVSRTQKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Ethyl (2E,4S,5R,6E)-5-Methoxy-2,4-dimethyl-7-phenyl-2,6-heptadienoate 在 Lindlar's catalyst 吡啶 、 咪唑 、 喹啉 、 lithium hydroxide 、 sodium periodate 、 四氧化锇 、 正丁基锂 、 zinc(II) tetrahydroborate 、 草酰氯 、 Proton Sponge 、 ammonium cerium(IV) nitrate 、 四丁基氟化铵 、 氢气 、 三甲基铝 、 双(2-氧代-3-恶唑烷基)次磷酰氯 、 四氯化钛 、 二异丁基氢化铝 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 三乙胺 、 N,N-二异丙基乙胺 、 环己烯 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 157.39h， 生成 Decarbamoyl (+)-Macbecin I
  参考文献：
  名称：

  Asymmetric synthesis of the benzoquinoid ansamycin antitumor antibiotics: total synthesis of (+)-macbecin

  摘要：

  A convergent asymmetric synthesis of the antitumor antibiotic macbecin I has been achieved. Six of the seven stereogenic centers within the target structure were controlled using asymmetric aldol methodology, while the final stereogenic center was established through internal asymmetric induction. Fragment coupling was accomplished using a mild, titanium tetrachloride mediated aldol reaction. The C1-C5 unsaturated dienic ester was stereoselectively incorporated through a kinetically controlled Horner-Emmons olefination. Macrolactamization and subsequent refunctionalization afforded macbecin I.

  DOI：

  10.1021/jo00054a035
• 作为产物：
  描述：

  (4R,5S)-3-<(2R,3R,4E)-3-Hydroxy-2-methyl-5-phenyl-4-pentenoyl>-4-methyl-5-phenyl-2-oxazolidinone 在 三甲基铝 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 13.5h， 生成 Ethyl (2E,4S,5R,6E)-5-Methoxy-2,4-dimethyl-7-phenyl-2,6-heptadienoate
  参考文献：
  名称：

  Asymmetric synthesis of the benzoquinoid ansamycin antitumor antibiotics: total synthesis of (+)-macbecin

  摘要：

  A convergent asymmetric synthesis of the antitumor antibiotic macbecin I has been achieved. Six of the seven stereogenic centers within the target structure were controlled using asymmetric aldol methodology, while the final stereogenic center was established through internal asymmetric induction. Fragment coupling was accomplished using a mild, titanium tetrachloride mediated aldol reaction. The C1-C5 unsaturated dienic ester was stereoselectively incorporated through a kinetically controlled Horner-Emmons olefination. Macrolactamization and subsequent refunctionalization afforded macbecin I.

  DOI：

  10.1021/jo00054a035

文献信息

• Asymmetric synthesis of macbecin I
  作者：David A. Evans、Scott J. Miller、Michael D. Ennis、Paul L. Ornstein

  DOI：10.1021/jo00030a006

  日期：1992.2

  The asymmetric synthesis of macbecin I is described wherein the absolute stereochemical relationships were established through the use of chiral boron aldol bond constructions and internally directed alpha-methoxy ketone reduction, while the E,Z dienic amide moiety was installed in one step using a vinylogous phosphonate reagent.
• Asymmetric synthesis of the benzoquinoid ansamycin antitumor antibiotics: total synthesis of (+)-macbecin
  作者：David A. Evans、Scott J. Miller、Michael D. Ennis

  DOI：10.1021/jo00054a035

  日期：1993.1

  A convergent asymmetric synthesis of the antitumor antibiotic macbecin I has been achieved. Six of the seven stereogenic centers within the target structure were controlled using asymmetric aldol methodology, while the final stereogenic center was established through internal asymmetric induction. Fragment coupling was accomplished using a mild, titanium tetrachloride mediated aldol reaction. The C1-C5 unsaturated dienic ester was stereoselectively incorporated through a kinetically controlled Horner-Emmons olefination. Macrolactamization and subsequent refunctionalization afforded macbecin I.