Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions.

ABSTRACT: We report an enantioselective synthesis of cyclic ketones with full substitutions at the α-positions in a highly diastereoselective manner. Our method is achieved by subjecting substrate motifs in 2-allyloxyenones to chiral organomagnesium reagents, which trigger the Claisen rearrangement upon direct 1,2-carbonyl addition. The observed diastereoselectivity of the allyl migration is proposed to originate from the intramolecular chelation of the magnesium alkoxide to the allyloxy moiety.

SUBMITTER: Badmus FO 

PROVIDER: S-EPMC10616857 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature