(3S)-4-(tert-butyldiphenylsilyloxy)-3-methyl-1-bromo-1-butyne | 1000600-57-6

• 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: (3S)-4-(tert-butyldiphenylsilyloxy)-3-methyl-1-bromo-1-butyne
• 英文别名: [(2S)-4-bromo-2-methylbut-3-ynoxy]-tert-butyl-diphenylsilane
• CAS: 1000600-57-6
• 化学式: C₂₁H₂₅BrOSi
• 分子量: 401.418
• InChiKey: CHYZRGNBAYTOHU-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.55
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3S)-4-(tert-butyldiphenylsilyloxy)-3-methyl-1-bromo-1-butyne 、 Dimethylzinc 在 二溴硼烷 、 碘 作用下， 以 二氯甲烷 、 甲苯 、 四氢呋喃 为溶剂， 反应 1.0h， 以81%的产率得到(2Z,4S)-5-(tert-butyldiphenylsilyloxy)-2-iodo-4-methyl-2-pentene
  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：

  (S)-tert-butyl((4,4-dibromo-2-methylbut-3-en-1-yl)oxy)diphenylsilane 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以91%的产率得到(3S)-4-(tert-butyldiphenylsilyloxy)-3-methyl-1-bromo-1-butyne
  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.