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A photoredox reaction for cross-dehydrogenative coupling (CDC) was developed to C α -arylate amides (α to nitrogen) and ethers using a variety of five- and six-membered electron-deficient heteroarenes. A unique decomposition mechanism of ammonium persulfate enhanced by photoexcited benzaldehydes was revealed. This benzaldehyde-mediated photoredox reaction proceeded smoothly with household 23 W CFL bulbs as the energy source under metal-free conditions, allowing the construction of new C sp 2  -C sp 2  and C sp 3  -C sp 2  bonds and access to important pharmacophores of broad utility using commercially available reagents.

Direct α-heteroarylation of amides (α to nitrogen) and ethers through a benzaldehyde-mediated photoredox reaction