Computational elucidation of the reaction mechanism for synthesis of pyrrolidinedione derivatives via Nef-type rearrangement - cyclization reaction.

ABSTRACT: This paper reports a quantum chemical study of all stages of a one-pot synthesis of pyrrolidinedione derivatives from nitromethane and coumarin, which includes Michael addition, migration of an oxygen atom (Nef-type rearrangement), and cyclization to a pyrrolidine ring. The energy barrier of deprotonated nitromethane addition to coumarin is 21.7 kJ mol^-1, while the barrier of proton transfer from the methylene to the nitro group in the nitromethyl group is notably higher, 197.8 kJ mol^-1. The second stage of the reaction, migration of an oxygen atom within the nitromethyl group, occurs with lowest energy barrier, 142.4 kJ mol^-1, when it is assisted by an additional water molecule. The last stage - cyclization, passes with a very low energy barrier of 11.9 kJ

SUBMITTER: Ilieva ED 

PROVIDER: S-EPMC9077586 | biostudies-literature | 2018 Jan

REPOSITORIES: biostudies-literature