A radical-based asymmetric olefin difunctionalization strategy for rapidly forging all-carbon quaternary stereocenters α to diverse azaarenes is reported. Under cooperative photoredox and chiral Brønsted acid catalysis, cyclopropylamines with αbranched 2-vinylazaarenes can undergo a sequential two-step radical process, furnishing various valuable chiral azaarene-substituted cyclopentanes. The use of the rigid and confined C 2 -symmetric imidodiphosphoric acid catalysts achieves high enantio-and diastereo-selectivities for these asymmetric [3 + 2] cycloadditions.

An enantioconvergent substitution of 3-substituted 3-chlorooxindoles with N-aryl glycines under visible light irradiation is reported.

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