Gwyndaf A Oliver, Konstantin Günther, Chiara Sebastianelli-Schoditsch, Sophie Woolford, Iina Ludwig, Harald H Sitte, Nuno Maulide
A redox-neutral hydroaminoalkylation strategy has been developed for the synthesis of 1,1-disubstituted aminocyclopropanes from alkenes and alkynes. Through simple solvolysis activation, the reaction of an easily accessible, bench-stable hemiaminal precursor allows excellent yields of the target products at ambient temperature. The approach presented herein has a substrate tolerance that is orthogonal to classical aminocyclopropane syntheses, and its deployment for the preparation of bioisosteres of pharmacologically active gem-α-dimethylamines resulted in improved biological properties.