posted on 2017-07-18, 00:00authored byChristina
H. McCulley, Michael J. Geier, Brandi M. Hudson, Michel R. Gagné, Dean J. Tantillo
Results of kinetic experiments and
quantum chemical computations
on a series of platinum-promoted polycyclization reactions are described.
Analyses of these results reveal a reactivity model that reaches beyond
the energetics of the cascade itself, incorporating an ensemble of
pre-cyclization conformations of the platinum–alkene reactant
complex, only a subset of which are productive for bi- (or larger)
cyclization and lead to products. Similarities and differences between
this scenario, including reaction coordinates for polycyclization,
for platinum- and enzyme-promoted polycyclization reactions are highlighted.