(3E,5Z,7R)-5-bromo-8-(tert-butyldimethylsilyloxy)-7-methyl-1-trimethylsilyl-3,5-octadien-1-yne | 627907-24-8

• 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: (3E,5Z,7R)-5-bromo-8-(tert-butyldimethylsilyloxy)-7-methyl-1-trimethylsilyl-3,5-octadien-1-yne
• 英文别名: (3E,5Z,7R)-5-bromo-8-(t-butyldimethylsilyloxy)-7-methyl-1-trimethylsilyl-3,5-octadien-1-yne；[(3E,5Z,7R)-5-bromo-8-[tert-butyl(dimethyl)silyl]oxy-7-methylocta-3,5-dien-1-ynyl]-trimethylsilane
• CAS: 627907-24-8
• 化学式: C₁₈H₃₃BrOSi₂
• 分子量: 401.534
• InChiKey: FBFRNRKSWAFUQH-TWQCNNRISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (3E,5Z,7R)-5-bromo-8-(tert-butyldimethylsilyloxy)-7-methyl-1-trimethylsilyl-3,5-octadien-1-yne 、 乙炔基溴化镁 在 Cl₂Pd[bis(2-diphenylphosphinophenyl) ether] 、 zinc dibromide 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 以96%的产率得到(3E,5E,7R)-1-trimethylsilyl-5-ethynyl-7-methyl-8-(tert-butyldimethylsilyloxy)-3,5-octadien-1-yne
  参考文献：
  名称：

  Clean Inversion of Configuration in the Pd-Catalyzed Cross-Coupling of 2-Bromo-1,3-dienes

  摘要：

  The Pd-catalyzed cross-coupling reaction of 2-bromo-1,3-dienes derived from alkyl aldehydes, especially with Cl2Pd(DPEphos) as a catalyst, proceeds with clean stereoinversion of the Br-bearing C=C bond to produce in high yields and in high stereoselectivity (>/=97-98%) conjugated Z,E dienes of potentially high utility in the synthesis of complex natural products. The observed stereoinversion cannot be readily accommodated by the widely accepted pi-sigma-pi rearrangement mechanism for isomerization of ordinary allylpalladium derivatives.

  DOI：

  10.1021/ja0304392
• 作为产物：
  描述：

  4-溴丁-3-烯-1-炔基(三甲基)硅烷 、 (3R)-1,1-dibromo-3-methyl-4-(tert-butyldimethylsilyloxy)-1-butene 在 叔丁基锂 、 zinc dibromide 、 四(三苯基膦)钯 作用下， 以 乙醚 、 正戊烷 、 四氢呋喃 为溶剂， 反应 4.0h， 以70%的产率得到(3E,5Z,7R)-5-bromo-8-(tert-butyldimethylsilyloxy)-7-methyl-1-trimethylsilyl-3,5-octadien-1-yne
  参考文献：
  名称：

  Clean Inversion of Configuration in the Pd-Catalyzed Cross-Coupling of 2-Bromo-1,3-dienes

  摘要：

  The Pd-catalyzed cross-coupling reaction of 2-bromo-1,3-dienes derived from alkyl aldehydes, especially with Cl2Pd(DPEphos) as a catalyst, proceeds with clean stereoinversion of the Br-bearing C=C bond to produce in high yields and in high stereoselectivity (>/=97-98%) conjugated Z,E dienes of potentially high utility in the synthesis of complex natural products. The observed stereoinversion cannot be readily accommodated by the widely accepted pi-sigma-pi rearrangement mechanism for isomerization of ordinary allylpalladium derivatives.

  DOI：

  10.1021/ja0304392

文献信息

• Highly Stereoselective Synthesis of (1E)-2-Methyl-1,3-dienes by Palladium-Catalyzedtrans-Selective Cross-Coupling of 1,1-Dibromo-1-alkenes with Alkenylzinc Reagents
  作者：Xingzhong Zeng、Mingxing Qian、Qian Hu、Ei-ichi Negishi

  DOI：10.1002/anie.200353022

  日期：2004.4.19
• Clean Inversion of Configuration in the Pd-Catalyzed Cross-Coupling of 2-Bromo-1,3-dienes
  作者：Xingzhong Zeng、Qian Hu、Mingxing Qian、Ei-ichi Negishi

  DOI：10.1021/ja0304392

  日期：2003.11.1

  The Pd-catalyzed cross-coupling reaction of 2-bromo-1,3-dienes derived from alkyl aldehydes, especially with Cl2Pd(DPEphos) as a catalyst, proceeds with clean stereoinversion of the Br-bearing C=C bond to produce in high yields and in high stereoselectivity (>/=97-98%) conjugated Z,E dienes of potentially high utility in the synthesis of complex natural products. The observed stereoinversion cannot be readily accommodated by the widely accepted pi-sigma-pi rearrangement mechanism for isomerization of ordinary allylpalladium derivatives.