Cooperative Hydrogen-Bond Pairing in Organocatalytic Ring-Opening Polymerization.
Thiourea (TU)/amine base cocatalysts are commonly employed for well-controlled, highly active "living" organocatalytic ring-opening polymerizations (ROPs) of cyclic esters and carbonates. In this work, several of the most active cocatalyst pairs are shown by1H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP. One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species. The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.
Department of Chemistry, University of Rhode Island , Kingston, Rhode Island 02881, United States.
Oleg I
OI
Kazakov
Department of Chemistry, University of Rhode Island , Kingston, Rhode Island 02881, United States.
Partha P
PP
Datta
Department of Chemistry, University of Rhode Island , Kingston, Rhode Island 02881, United States.
Meghedi
M
Isajani
Department of Chemistry, University of Rhode Island , Kingston, Rhode Island 02881, United States.
Elizabeth T
ET
Kiesewetter
Department of Chemistry, University of Rhode Island , Kingston, Rhode Island 02881, United States.
Matthew K
MK
Kiesewetter