Dimerization of confined Bronsted acids in enantioselective organocatalytic reactions.

ABSTRACT: The formation of Brønsted acid aggregates in the course of asymmetric organocatalytic reactions is often overlooked in mechanistic studies, even though it might have a deep impact on the stereo-controlling factors of the transformations. In this work, we shed light on the influence of the catalyst structure and reaction conditions on the spontaneity of the aggregation process for popular chiral organocatalysts derived from phosphoric acids using high-level quantum mechanical calculations. Our study encompasses small and sterically unhindered chiral phosphoric acids as well as large and "confined" imidodiphosphates and imidodiphosphorimidates. These systems have recently proven particularly effective in promoting a large number of highly relevant asymmetric transformations. While cooperativ

SUBMITTER: Harden I 

PROVIDER: S-EPMC10548523 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature