This review describes enzyme-catalyzed reactions involving ambimodal transition states, and recent advances in understanding how enzymes control selectivity in such reactions.
In the dynamically stepwise reaction pathway C–H insertion versus Cope selectivity is highly influenced by whether or not vibrational synchronization occurs in the nonstatistical entropic intermediate.
The asterisca-1,6-diene synthase from the liverwort Radula lindenbergiana was functionally and mechanistically characterised, with implications also for the long discussed biosynthesis of pentalenene.
Computations were used to model the rearrangement of the barbaralyl cation, a structure that demonstrates nonclassical bridging, homoconjugation, fluxionality, non-statistical dynamic effects, post-transition state bifurcations, and tunneling!