Preparation of Chiral Contiguous Epoxyaziridines and Their Regioselective Ring‐Opening for Drug Syntheses

Synthetically valuable chiral (aziridin‐2‐yl)oxirane‐3‐carbaldehydes bearing three consecutive functional groups including aziridine, epoxide, and aldehyde were prepared from the stereoselective epoxidation of (aziridin‐2‐yl)acrylaldehydes with H2O2 using organocatalyst (2R)‐ or (2S)‐[diphenyl(trimethylsilyloxy)methyl]pyrrolidine as organocatalyst. The regioselective ring opening of aziridines and epoxides enabled us to achieve the highly efficient asymmetric synthesis of the antibiotic edeine D fragment 3‐hydroxy‐4,5‐diaminopenatanoic acid, an intermediate for the formal synthesis of non‐proteinogenic amino acid (−)‐galantinic acid, and for potent antifungal agent (+)‐preussin, and the medicinally important framework 3‐hydroxy‐2‐hydroxymethylpyrrolidine. Aziridine and epoxide: This work reports the preparation of a contiguous epoxyaziridine in its optically pure form and its use in the asymmetric synthesis of various biologically active oxygenated amines using sequential and selective ring‐opening reactions.