ethyl 6-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-methyl-2(E),4(E),6(Z)-octatrienoate | 146983-18-8

• 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 6-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-methyl-2(E),4(E),6(Z)-octatrienoate
• 英文别名: ethyl (2E,4E,6Z)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methylocta-2,4,6-trienoate
• CAS: 146983-18-8
• 化学式: C₂₈H₃₆O₃Si
• 分子量: 448.678
• InChiKey: MIHFCHPXBJTHJO-ZDRZPRIRSA-N

物化性质

• 沸点：
  515.1±50.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.57
• 重原子数：
  32
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 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 6-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-methyl-2(E),4(E),6(Z)-octatrienoate 在 咪唑 、 4-二甲氨基吡啶 、 草酰氯 、 2,6-二叔丁基-4-甲基苯酚 、 二异丁基氢化铝 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 67.0h， 生成 methyl(1S,2S,5R)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-1-acetoxy-5-methyl-2-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>-3-cyclohexene-1-carboxylate
  参考文献：
  名称：

  A highly diastereo- and enantioselective synthesis of the top half of kijanolide

  摘要：

  A highly diastereo- and enantioselective synthesis of spirotetronate 4 corresponding to the top half of kijanolide is reported. This synthesis features the novel exo-selective Diels-Alder reaction of triene 6 and the chiral, nonracemic dienophiles (R)-7 and (R)-8. The reaction of 6 and (R)-7 produced a mixture of the desired exo cycloadduct 28, the unexpected exo diastereofacial isomer 29, and a minor amount of the endo cycloadduct 30. However, the Diels-Alder reaction of 6 and dienophile (R)-8 with the more sterically demanding tert-butyl substituent provided a 13-14:1 mixture of exo cycloadduct 38 and endo isomer 39; the exo diastereofacial isomer corresponding to 29 was not observed. Elaboration of 28 and 38 to spirotetronate 4 proceeded by way of the Dieckmann cyclization of alpha-acetoxy ester 5.

  DOI：

  10.1021/jo00060a035
• 作为产物：
  描述：

  methyl (2E)-2-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-butenoate 在 manganese(IV) oxide 、 二异丁基氢化铝 、 lithium hexamethyldisilazane 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 115.25h， 生成 ethyl 6-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-methyl-2(E),4(E),6(Z)-octatrienoate
  参考文献：
  名称：

  A highly diastereo- and enantioselective synthesis of the top half of kijanolide

  摘要：

  A highly diastereo- and enantioselective synthesis of spirotetronate 4 corresponding to the top half of kijanolide is reported. This synthesis features the novel exo-selective Diels-Alder reaction of triene 6 and the chiral, nonracemic dienophiles (R)-7 and (R)-8. The reaction of 6 and (R)-7 produced a mixture of the desired exo cycloadduct 28, the unexpected exo diastereofacial isomer 29, and a minor amount of the endo cycloadduct 30. However, the Diels-Alder reaction of 6 and dienophile (R)-8 with the more sterically demanding tert-butyl substituent provided a 13-14:1 mixture of exo cycloadduct 38 and endo isomer 39; the exo diastereofacial isomer corresponding to 29 was not observed. Elaboration of 28 and 38 to spirotetronate 4 proceeded by way of the Dieckmann cyclization of alpha-acetoxy ester 5.

  DOI：

  10.1021/jo00060a035

文献信息

• ROUSH, WILLIAM R.;BROWN, BRADLEY B., TETRAHEDRON LETT., 30,(1989) N2, C. 7309-7312
  作者：ROUSH, WILLIAM R.、BROWN, BRADLEY B.

  DOI：——

  日期：——