methyl (2E,4E,6Z,8S)-9-[tert-butyl(diphenyl)silyl]oxy-4,6,8-trimethylnona-2,4,6-trienoate | 1000600-64-5

• 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: methyl (2E,4E,6Z,8S)-9-[tert-butyl(diphenyl)silyl]oxy-4,6,8-trimethylnona-2,4,6-trienoate
• CAS: 1000600-64-5
• 化学式: C₂₉H₃₈O₃Si
• 分子量: 462.704
• InChiKey: HDDQIQARRAAUHW-MOSXPYDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.82
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (2Z,4S)-5-(tert-butyldiphenylsilyloxy)-2-iodo-4-methyl-2-pentene 、 methyl (2E,4E)-5-iodo-4-methyl-2,4-pentadienoate 在 四(三苯基膦)钯 叔丁基锂 、 zinc dibromide 作用下， 以 乙醚 、 正戊烷 、 四氢呋喃 为溶剂， 反应 5.17h， 以63%的产率得到methyl (2E,4E,6Z,8S)-9-[tert-butyl(diphenyl)silyl]oxy-4,6,8-trimethylnona-2,4,6-trienoate
  参考文献：
  名称：

  Highly Stereo- and Regioselective Synthesis of (Z)-Trisubstituted Alkenes via 1-Bromo-1-alkyne Hydroboration−Migratory Insertion−Zn-Promoted Iodinolysis and Pd-Catalyzed Organozinc Cross-Coupling

  摘要：

  Hydroboration of 1-bromo-1-alkynes with dibromoborane followed by addition of 3 or 4 equiv of Me2Zn provides an efficient and selective route to (Z)-2-alkenyldimethylboranes (3) or (Z)-2-alkenylmethylzincs (4), respectively, which have been successfully applied to one-pot Suzuki (B-I) or Negishi (Zn-I) coupling in some less demanding cases. However, in more demanding cross-coupling reactions, only the use of either (Z)-2-alkenyliodides (5) or the alkenylzincs prepared from lithiation and then zincation of 5 proves to be highly satisfactory (Zn-II or Zn-III protocol). On the contrary, the corresponding organoboron coupling under B-II or B-III protocol appears to be less satisfactory. Preliminary studies indicate that certain substituents proximal to trisubstituted alkenes seriously affect the course of the desired alkenylboron crosscoupling.

  DOI：

  10.1021/ja0772039

文献信息

• Highly Stereo- and Regioselective Synthesis of (<i>Z</i>)-Trisubstituted Alkenes via 1-Bromo-1-alkyne Hydroboration−Migratory Insertion−Zn-Promoted Iodinolysis and Pd-Catalyzed Organozinc Cross-Coupling
  作者：Zhihong Huang、Ei-ichi Negishi

  DOI：10.1021/ja0772039

  日期：2007.11.28

  Hydroboration of 1-bromo-1-alkynes with dibromoborane followed by addition of 3 or 4 equiv of Me2Zn provides an efficient and selective route to (Z)-2-alkenyldimethylboranes (3) or (Z)-2-alkenylmethylzincs (4), respectively, which have been successfully applied to one-pot Suzuki (B-I) or Negishi (Zn-I) coupling in some less demanding cases. However, in more demanding cross-coupling reactions, only the use of either (Z)-2-alkenyliodides (5) or the alkenylzincs prepared from lithiation and then zincation of 5 proves to be highly satisfactory (Zn-II or Zn-III protocol). On the contrary, the corresponding organoboron coupling under B-II or B-III protocol appears to be less satisfactory. Preliminary studies indicate that certain substituents proximal to trisubstituted alkenes seriously affect the course of the desired alkenylboron crosscoupling.