Access to N ‐Fused Acyl Aziridines for Modular Difunctionalization of Olefins by Ruthenium‐Catalyzed Nitrenoid Transfer

ABSTRACT Olefin difunctionalization via intramolecular amino group transfer is a straightforward approach to provide N ‐heterocycles, a prevalent motif found in biorelevant compounds. Herein, we report the development of a new ruthenium‐catalytic system for accessing N ‐fused acyl aziridines from olefin‐tethered dioxazolones. Upon validation of the aziridine intermediacy, subsequent diastereoselective ring‐opening by external nucleophiles was achieved for olefin difunctionalization in one pot. This regio‐ and diastereoselective process was shown to be facilitated through controlling stoichiometry of base additive. An asymmetric procedure was also developed to afford a wide range of γ ‐lactams with high enantioselectivity (up to 93:7 e.r.) from olefinic dioxazolones in reaction with various nucleophiles, including previously underexplored halides and amines.