Decoded fingerprints of hyperresponsive, expanding product space: polyether cascade cyclizations as tools to elucidate supramolecular catalysis.

ABSTRACT: Simple enough to be understood and complex enough to be revealing, cascade cyclizations of diepoxides are introduced as new tools to characterize supramolecular catalysis. Decoded product fingerprints are provided for a consistent set of substrate stereoisomers, and shown to report on chemo-, diastereo- and enantioselectivity, mechanism and even autocatalysis. Application of the new tool to representative supramolecular systems reveals, for instance, that pnictogen-bonding catalysis is not only best in breaking the Baldwin rules but also converts substrate diastereomers into completely different products. Within supramolecular capsules, new cyclic hemiacetals from House-Meinwald rearrangements are identified, and autocatalysis on anion-π catalysts is found to be independent of substrate st

SUBMITTER: Chen H 

PROVIDER: S-EPMC9473502 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature