Doyle, MichaelMarichev, KostiantynDong, KuiyongMassey, LynéeDeng, YongmingDe Angelis, LucaWang, KanArman, Hadi2021-11-152021-11-152019-11-221476-4687https://hdl.handle.net/20.500.12588/715Coupling reactions of amines and alcohols are of central importance for applications in chemistry and biology. These transformations typically involve the use of a reagent, activated as an electrophile, onto which nucleophile coupling results in the formation of a carbon-nitrogen or a carbon–oxygen bond. Several promising reagents and procedures have been developed to achieve these bond forming processes in high yields with excellent stereo-control, but few offer direct coupling without the intervention of a catalyst. Herein, we report the synthesis of chiral donor–acceptor azetines by highly enantioselective [3 + 1]-cycloaddition of enoldiazoacetates with aza-ylides and their selective coupling with nitrogen and oxygen nucleophiles via 3-azetidinones to form amino acid derivatives, including those of peptides and natural products. The overall process is general for a broad spectrum of nucleophiles, has a high degree of electronic and steric selectivity, and retains the enantio-purity of the original azetine.en-USAttribution 3.0 United Stateshttp://creativecommons.org/licenses/by/3.0/us/Article