In addition to expanding the catalytic repertoire of dienamine organocatalysis, this Claisen rearrangement was conceived to assess the feasibility of DyKAT of γ-epimeric enals via dienamine formation and concomitant intramolecular proximal functionalization to produce enantioenriched products. Mechanistic studies support a DyKAT. For the first time, a reactive dienamine intermediate has been isolated, fully characterized, and resubjected to reaction conditions to generate product, in further support of this mechanistic hypothesis. γ-Aryl and alkyl enals, and exocyclic enals that afford products with quaternary chiral centers, are all suitable substrates for this transformation. Acyclic products can be converted in one step into substituted pyrrolidines or cyclopentenols. Computations revealed that product configuration arises from a directing C-H…π interaction in the transition state, which is arguably an underexploited mode of asymmetric induction in catalysis.

DyKAT by DiCat: A stereoconvergent dienamine-catalyzed Claisen rearrangement

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.