Gold for the generation and control of fluxional barbaralyl cations

Paul R. McGonigal*, Claudia De León, Yahui Wang, Anna Homs, César R. Solorio-Alvarado, Antonio M. Echavarren

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Fluxional molecules which rapidly pass back and forth between a large number of constitutional isomers through low-energy rearrangements have fascinated chemists owing to their role in the study of fundamental theoretical concepts[ 2] and their potential to adapt their chemical structures in response to their environment or to act as prototypical molecular transport systems. They represent a facet of systems chemistry that is relatively unexplored, in which a dynamic structural library can be contained within a single molecule. The 9-barbaralyl cation (1) is a hugely fluxional C9H9 + hydrocarbon that exists as a mixture of 181 400 degenerate forms which interconvert rapidly at temperatures as low as -135 °C-each carbon atom may exchange with every other carbon atom in the structure through a series of pericyclic reactions. Unlike the neutral homologues semibullvalene (2; two degenerate tautomers) and bullvalene (3; 1209600 degenerate tautomers), which are stable compounds under ambient conditions, 1 is highly reactive and undergoes irreversible rearrangement to 1,4-bishomotropylium cation (4) above -125 °C. Functionalized barbaralanes may be suitable candidates for switchable, fluxional molecules. However, the difficulty in handling these compounds coupled with the low-yielding, multistep syntheses and harsh reaction conditions (typically featuring strongly or super acidic media) employed in the generation of 1 and its derivatives have so far limited the extent to which the chemistry of this fascinating dynamic carbon skeleton has been explored.

Original languageEnglish
Pages (from-to)13093-13096
Number of pages4
JournalAngewandte Chemie - International Edition
Issue number52
Publication statusPublished - 21 Dec 2012


  • Barbaralyl cations
  • Cyclization
  • Enynes
  • Fluxionality
  • Gold catalysis

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