Bis(2,2,2-trifluoroethyl) 3-(methoxycarbonyl)-3-methylprop-2-enylphosphonate | 138694-12-9

• 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: Bis(2,2,2-trifluoroethyl) 3-(methoxycarbonyl)-3-methylprop-2-enylphosphonate
• 英文别名: methyl (E)-4-[bis(2,2,2-trifluoroethoxy)phosphoryl]-2-methylbut-2-enoate
• CAS: 138694-12-9
• 化学式: C₁₀H₁₃F₆O₅P
• 分子量: 358.174
• InChiKey: WCEQAZOJVGBJPS-XVNBXDOJSA-N

物化性质

• 沸点：
  308.4±42.0 °C(Predicted)
• 密度：
  1.376±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  Bis(2,2,2-trifluoroethyl) 3-(methoxycarbonyl)-3-methylprop-2-enylphosphonate 在 Lindlar's catalyst 喹啉 、 lithium hydroxide 、 正丁基锂 、 ammonium cerium(IV) nitrate 、 四丁基氟化铵 、 氢气 、 双(2-氧代-3-恶唑烷基)次磷酰氯 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 106.5h， 生成 [(2R,3S,6S,7R,8E,11S,12Z,14E)-2,5,6-三甲氧基-3,7,9,11,15-五甲基-16,20,22-三氧代-17-氮杂双环[16.3.1]二十二-1(21),8,12,14,18-五烯-10-基]氨基甲酸酯
  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：

  (2E)-trimethyl phosphono 2-methylbut-2-enoate 在 五氯化磷 、 N,N-二异丙基乙胺 作用下， 以 苯 为溶剂， 反应 21.5h， 生成 Bis(2,2,2-trifluoroethyl) 3-(methoxycarbonyl)-3-methylprop-2-enylphosphonate
  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

• An improved synthesis of the (E,Z)-dienoate precursor of (+)-damavaricin D via a vinylogous Horner-Wadsworth-Emmons reaction
  作者：Sherry R. Chemler、D.Scott Coffey、William R. Roush

  DOI：10.1016/s0040-4039(98)02638-0

  日期：1999.2

  An improved synthesis of the C(1)–C(5) (E,Z)-dienoate segment of (+)-damavaricin D precursor 3 was accomplished using the unsaturated phosphonate reagent 9 in a (Z)-selective vinylogous Horner-Wadsworth-Emmons reaction.

  在（Z）选择性黑胶质Horner-Wadsworth中使用不饱和膦酸酯试剂9改进了（+）-达马曲霉素D前体3的C（1）–C（5）（E，Z）-二烯二酸酯部分的合成-表情反应。
• 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.