r-1-butyl-1-(2-methyl-1-propenyl)-c-2-phenylcyclopropane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: r-1-butyl-1-(2-methyl-1-propenyl)-c-2-phenylcyclopropane
• 英文别名: [(1R,2S)-2-butyl-2-(2-methylprop-1-enyl)cyclopropyl]benzene
• 化学式: C₁₇H₂₄
• 分子量: 228.378
• InChiKey: UPPOPFUXXYUVJH-DLBZAZTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  正丁基锂 、 1-溴-2-甲基-1-丙烯 、 (2,2-二溴环丙基)苯 生成 r-1-butyl-1-(2-methyl-1-propenyl)-c-2-phenylcyclopropane 、 r-1-butyl-1-(2-methyl-1-propenyl)-t-2-phenylcyclopropane
  参考文献：
  名称：

  Stereoselective carbon-carbon bond-forming reaction of 1,1-dibromocyclopropanes via 1-halocyclopropylzincates

  摘要：

  Lithium trialkylzincates react efficiently with 1,1-dibromocyclopropanes 5 to give the corresponding alkylation products 7 nonstereoselectively. The reaction proceeds through a 1,2-alkyl migration of the intermediately formed zincate carbenoid 3 in an invertive manner. Reaction of 5 with BuLi followed by successive treatment of the resulting trans-lithium carbenoid 8 with ZnCl2 and an alkyllithium (R2Li) produces the zincate carbenoid trans-3, which, in turn, gives cis-7 stereoselectively (Method B). Reaction of lithium trialkylzincates and trans-1-bromo-1-chlorocyclopropanes 11 prepared in situ by chlorination of the trans-lithium carbenoid with CF2ClCFCl2 yields trans-7 stereoselectively (Method C). 1-Alkylcyclopropylzinc 4, an intermediate of the alkylation reaction, reacts smoothly with acyl, aryl, and alkenyl halides in the presence of a palladium(0) catalyst to give the corresponding coupling products 15 and 16. By generating the cyclopropylzinc intermediate 4 stereoselectively by using method B or C, one can obtain the desired stereoisomers of the coupling products with high selectivity.

  DOI：

  10.1021/jo00063a010

文献信息

• Stereoselective carbon-carbon bond-forming reaction of 1,1-dibromocyclopropanes via 1-halocyclopropylzincates
  作者：Toshiro Harada、Takeshi Katsuhira、Kazuhiro Hattori、Akira Oku

  DOI：10.1021/jo00063a010

  日期：1993.5

  Lithium trialkylzincates react efficiently with 1,1-dibromocyclopropanes 5 to give the corresponding alkylation products 7 nonstereoselectively. The reaction proceeds through a 1,2-alkyl migration of the intermediately formed zincate carbenoid 3 in an invertive manner. Reaction of 5 with BuLi followed by successive treatment of the resulting trans-lithium carbenoid 8 with ZnCl2 and an alkyllithium (R2Li) produces the zincate carbenoid trans-3, which, in turn, gives cis-7 stereoselectively (Method B). Reaction of lithium trialkylzincates and trans-1-bromo-1-chlorocyclopropanes 11 prepared in situ by chlorination of the trans-lithium carbenoid with CF2ClCFCl2 yields trans-7 stereoselectively (Method C). 1-Alkylcyclopropylzinc 4, an intermediate of the alkylation reaction, reacts smoothly with acyl, aryl, and alkenyl halides in the presence of a palladium(0) catalyst to give the corresponding coupling products 15 and 16. By generating the cyclopropylzinc intermediate 4 stereoselectively by using method B or C, one can obtain the desired stereoisomers of the coupling products with high selectivity.