1-(tert-butyldimethylsilyloxy)-3-(dibromomethylene)-hex-5-ene

• 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: 1-(tert-butyldimethylsilyloxy)-3-(dibromomethylene)-hex-5-ene
• 英文别名: Tert-butyl-[3-(dibromomethylidene)hex-5-enoxy]-dimethylsilane
• 化学式: C₁₃H₂₄Br₂OSi
• 分子量: 384.226
• InChiKey: ZDECSNCOWTVAHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.98
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  4-(叔丁基二甲基硅杂氧基)-1-丁炔 、 3-溴丙烯 在 indium 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以72%的产率得到1-(tert-butyldimethylsilyloxy)-3-(dibromomethylene)-hex-5-ene
  参考文献：
  名称：

  Carboindation of Carbon−Carbon Triple Bonds:  Regioselective Indium-Mediated Allylation of Functionalized Alkynes and Transformation into Halogen-Substituted 1,4-Dienes

  摘要：

  By examining the allylindation of a series of substituted alkynes, the relationships between allylindation reactivity and alkyne structure were systematically investigated. While terminal alkynes with protected hydroxyl groups gave the corresponding allylated branched 1,4-dienes (Markovnikov products) within 5-6 h, the unprotected alkynols reacted markedly faster, requiring only 2-4 h of ultrasonication in THF to produce the 1,4-dienols in good yields. In the latter reactions, the regioisomeric outcome was found to depend on the distance between the hydroxyl group and the alkyne moiety: propargylic substrates gave linear 1,4-dienes (anti-Markovnikov products), suggesting the involvement of bicyclic "chelation-controlled" transition state, while 4-pentynol and higher homologues exclusively afforded the branched 1,4-dienes. Moreover, the proposed vinylic alpha,alpha-bis-indium intermediates from both protected and unprotected substrates were successfully quenched with N-bromosuccinimide (NBS) and N-iodosuccinimide (NIS) to form tri- and tetrasubstituted dienes in good yields. Taken as a whole, these results illustrate the remarkable stability of the allylindium and vinylindium intermediates despite the presence of protic functionalities in the reaction mixture.

  DOI：

  10.1021/jo9908593

文献信息

• Carboindation of Carbon−Carbon Triple Bonds:  Regioselective Indium-Mediated Allylation of Functionalized Alkynes and Transformation into Halogen-Substituted 1,4-Dienes
  作者：Ernst Klaps、Walther Schmid

  DOI：10.1021/jo9908593

  日期：1999.10.1

  By examining the allylindation of a series of substituted alkynes, the relationships between allylindation reactivity and alkyne structure were systematically investigated. While terminal alkynes with protected hydroxyl groups gave the corresponding allylated branched 1,4-dienes (Markovnikov products) within 5-6 h, the unprotected alkynols reacted markedly faster, requiring only 2-4 h of ultrasonication in THF to produce the 1,4-dienols in good yields. In the latter reactions, the regioisomeric outcome was found to depend on the distance between the hydroxyl group and the alkyne moiety: propargylic substrates gave linear 1,4-dienes (anti-Markovnikov products), suggesting the involvement of bicyclic "chelation-controlled" transition state, while 4-pentynol and higher homologues exclusively afforded the branched 1,4-dienes. Moreover, the proposed vinylic alpha,alpha-bis-indium intermediates from both protected and unprotected substrates were successfully quenched with N-bromosuccinimide (NBS) and N-iodosuccinimide (NIS) to form tri- and tetrasubstituted dienes in good yields. Taken as a whole, these results illustrate the remarkable stability of the allylindium and vinylindium intermediates despite the presence of protic functionalities in the reaction mixture.