V. Aviyente

The mechanism of ring–chain–ring tautomerization and the prominent effect of the solvent environment have been computationally investigated in an effort to explain the enantiomeric interconversion observed in 2-oxazolidinone derivatives, heterocyclic analogues of biphenyl atropisomers, which were isolated as single stable enantiomers and have the potential to be used as axially chiral catalysts. This study has shed light on the identity of the intermediate species involved in the ring–chain–ring tautomerization process as well as the catalytic effect of polar protic solvents. These mechanistic details will prove very useful in predicting and understanding ring–chain tautomeric equilibria in similar heterocyclic systems and will further enable experimentalists to devise appropriate experimental conditions in which axially chiral catalysts remain stable as single enantiomers.

Radical polymerization processes occur through a complex network of many different reactions. It is well-known that the polymerization rate is directly related to the monomer structure. The experimental polymerizability behavior is expressed as kp/kt1/2, where kp is the rate coefficient of propagation and kt is the rate coefficient of termination. In this study, the reactivity of a series of acrylates and methacrylates is modeled in order to understand the effect of the pendant group size, the polarity of a pendant group, and the nature of the pendant group (linear vs cyclic) on their polymerizability. The geometries and frequencies are calculated with the B3LYP/6-31+G(d) methodology whereas the energetics and kinetics of these monomers have been studied using the two-component BMK/6-311+G(3df,2p)//B3LYP/6-31+G(d) level of theory. For rotations about forming/breaking bonds in the transition state, an uncoupled scheme for internal rotations has been applied with potentials determined at the B3LYP/6-31+G(d) level. Generally the rate constants for propagation kp mimic the qualitative polymerization trend of the monomers modeled and can be used with confidence in predicting the polymerizability behavior of acrylates. However in the case of 2-dimethylaminoethyl acrylate, chain transfer is found to play a major role in inhibiting the polymerization. On the other hand, the disproportionation reaction turns out to be too slow to be taken into consideration as a termination reaction.

The alcoholysis of cyclic meso-anhydrides catalyzed by β-amino alcohols has been investigated with DFT quantum mechanics to determine the mechanism of this reaction. Both nucleophilic catalysis and general base catalysis pathways are explored for methanol-induced ring opening of an anhydride catalyzed by a chiral amino alcohol. The nucleophilic pathway involves a late transition state with a high energy barrier. In this mechanism, methanolysis is expected to take place following the amine-induced ring opening of the anhydride. In the base-catalyzed mechanism, methanol attack on one carbonyl group of the meso-anhydride is assisted by the β-amino alcohol; the amine functionality abstracts the methanol proton. The chiral amino alcohol also catalyzes the reaction by stabilizing the oxyanion that forms upon ring opening of the anhydride by hydrogen bonding with its alcoholic moiety. Both stepwise and concerted pathways have been studied for the general base catalysis route. Transition structures for both are found to be lower in energy than in the nucleophilic mechanism. Overall this study has shed light on the mechanism of the β-amino alcohol-catalyzed alcoholysis of cyclic meso-anhydrides, showing that the nucleophilic pathway is approximately 100 kJ mol−1 higher in energy than the general base pathway.