Sigmatropic [1,3]-boron shift (permanent allylic rearrangement) in 3-allyl-3-borabicyclo[3.3.1]nonanes

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• 作者：M. E. Gurskii ; P. A. Belyakov ; K. A. Lyssenko ; A. L. Semenova…
• 关键词：allylic organoboranes ; allylboron ; acetylene condensation ; dynamic NMR ; 3 ; borabicyclo[3.3.1]nonanes
• 刊名：Russian Chemical Bulletin
• 出版年：2014
• 出版时间：February 2014
• 年：2014
• 卷：63
• 期：2
• 页码：480-486
• 全文大小：319 KB
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• 作者单位：M. E. Gurskii (1)
  P. A. Belyakov (1)
  K. A. Lyssenko (2)
  A. L. Semenova (1)
  Yu. N. Bubnov (1) (2)
  
  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation
  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation
  
• ISSN：1573-9171

文摘

2D 1H-1H EXSY NMR spectroscopy show that the free energy of activation ΔG ?/sup> in six 3-allyl-3-borabicyclo[3.3.1]nonane derivatives is significantly higher (72-6 kJ mol?) than that in typical allylboranes (48-6 kJ mol?). For the first member of the series, viz., 3-allyl-3-borabicyclo[3.3.1]nonane, the activation parameters of the permanent allylic rearrangement were also determined (ΔH ?/sup> = 82.7±3.4 kJ mol?, ΔS ?/sup> = ?1.8±10.3 J mol? K?, E A = 85.5±3.4 kJ mol?, lnA = 29.2±1.2).