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The ubiquity of sulfur‐containing molecules in biologically active natural products and pharmaceuticals has long attracted synthetic chemists to develop efficient strategies towards their synthesis. The strategy of direct α‐C(sp3)−H modification of sulfides provides a streamlining access to complex sulfur‐containing molecules. Herein, we report a photoinduced chemo‐, site‐ and stereoselective α‐C(sp3)−H functionalization of sulfides using isatins as the photoredox reagent and coupling partner catalyzed by a chiral gallium(III)‐N,N′‐dioxide complex. The reaction proceeds through a verified single‐electron transfer (SET) mechanism with high efficiency, excellent functional group tolerance, as well as a broad substrate scope. Importantly, this cross‐coupling protocol is highly selective for the direct late‐stage functionalization of methionine‐related peptides, regardless of the inherent structural similarity and complexity of diverse residues. [ABSTRACT FROM AUTHOR]

Highly efficient kinetic resolution of 2 H-azirines by an asymmetric imine amidation was achieved in the presence of a chiral N, N′-dioxide/ScIII complex, thus providing a promising method to obtain the enantioenriched 2 H-azirine derivatives and protecting-group free aziridines at the same time. It is rare to find an example of N1 of an oxindole participating in a reaction over C3. Moreover, chiral 2 H-azirines were stereospecifically transformed into an unprotected aziridine and α-amino ketone. [ABSTRACT FROM AUTHOR]