Vinyl carbocations: solution studies of alkenyl(aryl)iodonium triflate fragmentations.

Abstract

Generation of vinyl cations is facile by fragmentation of alkenyl(aryl)iodonium trifluoromethanesulfonates. Kinetics and electronic effects were probed by (1)H NMR spectroscopy in CDCl(3). Products of fragmentation include six enol triflate isomers in addition to iodoarenes. The enol triflates arise from direct reaction of a triflate anion with the starting iodonium salts as well as triflate reaction with rearranged secondary cations derived from those salts. G2 calculations of the theoretical isodesmic hydride-transfer reaction between secondary vinyl cation 7 and primary vinyl cation 6 reveal that cation 6 is 17.8 kcal/mol higher in energy. Activation parameters for fragmentation of (Z)-2-ethyl-1-hexenyl(3,5-bis-trifluoromethylphenyl)iodonium triflate, 17e, were calculated using the Arrhenius equation: E(a) = 26.8 kcal/mol, Delta H(++) = 26.2 kcal/mol, and Delta S(++) = 11.9 cal/mol x K. Added triflate increases the rate of fragmentation slightly, and it is likely that for most beta,beta-dialkyl- substituted vinylic iodonium triflates enol triflate fragmentation products are derived from three competing mechanisms: (a) vinylic S(N)()2 substitution; (b) ligand coupling (LC); and (c) concerted aryliodonio departure and 1,2-alkyl shift leading to secondary rather than primary vinyl cations.