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

Authors
  • Gurskii, M. E.1
  • Belyakov, P. A.1
  • Lyssenko, K. A.2
  • Semenova, A. L.1
  • Bubnov, Yu. N.1, 2
  • 1 Russian Academy of Sciences, N. D. Zelinsky Institute of Organic Chemistry, 47 Leninsky prosp., Moscow, 119991, Russian Federation , Moscow (Russia)
  • 2 Russian Academy of Sciences, A. N. Nesmeyanov Institute of Organoelement Compounds, 28 ul. Vavilova, Moscow, 119991, Russian Federation , Moscow (Russia)
Type
Published Article
Journal
Russian Chemical Bulletin
Publisher
Springer US
Publication Date
Feb 01, 2014
Volume
63
Issue
2
Pages
480–486
Identifiers
DOI: 10.1007/s11172-014-0456-3
Source
Springer Nature
Keywords
License
Yellow

Abstract

2D 1H-1H EXSY NMR spectroscopy show that the free energy of activation ΔG≠ in six 3-allyl-3-borabicyclo[3.3.1]nonane derivatives is significantly higher (72–86 kJ mol−1) than that in typical allylboranes (48–66 kJ mol−1). 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≠ = 82.7±3.4 kJ mol−1, ΔS≠ = −11.8±10.3 J mol−1 K−1, EA = 85.5±3.4 kJ mol−1, lnA = 29.2±1.2).

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