DyKAT by DiCat: Stereoconvergent Dienamine-Catalyzed Claisen Rearrangements

• DOI: 10.1021/acs.joc.2c01079
• Publication Date: 2022-07-26T13:52:41Z
• Authors: Ana De Oliveira S...; Jordan L. Harper; Katherine N. Fuhr; Roger A. Lalancette; Paul Ha-Yeon Cheong; Stacey E. Brenner...
• Keywords: Stereoisomerism; 01 natural sciences; Catalysis; 0104 chemical sciences

This Claisen rearrangement establishes the feasibility of DyKAT of γ-epimeric enals via dienamine formation to afford enantioenriched products. γ-Aryl and -alkyl enals, and exocyclic enals that introduce quaternary centers, are all amenable substrates. Products are readily converted into pyrrolidines or cyclopentenols. Notably, a reactive dienamine intermediate has been isolated from a catalytic reaction, fully characterized, and converted to product upon reexposure to reaction conditions. Product configuration arises from a directing C-H···π interaction in the transition state.