tert-butyl-[(2S,3Z,5E)-7-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethylhepta-3,5-dienoxy]-diphenylsilane | 1000600-66-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tert-butyl-[(2S,3Z,5E)-7-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethylhepta-3,5-dienoxy]-diphenylsilane
• CAS: 1000600-66-7
• 化学式: C₃₁H₄₈O₂Si₂
• 分子量: 508.892
• InChiKey: ADKUCAHDNMMCHI-XKJUYPMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.72
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl-[(2S,3Z,5E)-7-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethylhepta-3,5-dienoxy]-diphenylsilane 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 生成 (2E,4Z,6S)-7-[tert-butyl(diphenyl)silyl]oxy-4,6-dimethylhepta-2,4-dien-1-ol
  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
• 作为产物：
  描述：

  (2Z,4S)-5-(tert-butyldiphenylsilyloxy)-2-iodo-4-methyl-2-pentene 、 (E)-1-tert-butyldimethylsilyloxy-3-iodo-2-propene 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 6.17h， 生成 tert-butyl-[(2S,3Z,5E)-7-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethylhepta-3,5-dienoxy]-diphenylsilane
  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.