79449-06-2Relevant articles and documents
Gold(I) carbenes by retro-buchner reaction: Generation and fate
Wang, Yahui,McGonigal, Paul R.,Herle, Bart,Besora, Maria,Echavarren, Antonio M.
, p. 801 - 809 (2014/02/14)
The fate of the aryl gold(I) carbenes generated by retro-Buchner reaction of ortho-substituted 7-aryl-1,3,5-cycloheptatrienes is dependent on the constitution of the ortho substituent. Indenes and fluorenes are obtained by intramolecular reaction of highly electrophilic gold(I) carbenes with alkenes and arenes. According to density functional theory calculations, the gold-catalyzed retro-Buchner process occurs stepwise, although the two carbon-carbon cleavages occur on a rather flat potential energy surface.
Gold for the generation and control of fluxional barbaralyl cations
McGonigal, Paul R.,De Leon, Claudia,Wang, Yahui,Homs, Anna,Solorio-Alvarado, Cesar R.,Echavarren, Antonio M.
, p. 13093 - 13096 (2013/03/13)
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.
Response of Acidity and Magnetic Rtesonance Properties to Aryl Substitution in Carbon Acids and Derived Carbanions: 2- and 3-Arylindenes
Greifenstein, Linda G.,Lambert, Joseph B.,Nienhuis, Ronald J.,Fried, Herbert E.,Pagani, Giorgio A.
, p. 5125 - 5132 (2007/10/02)
Substitution in the aryl ring of 2- and 3-arylindenes has been used to examine the acidity of these hydrocarbons and the charge density and ion pair structure of their anions.Acidities were measured for the 2-arylindenes both in pure Me2SO and in Me2SO-H2
