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A photoredox catalytic aliphatic C(sp3)–H thiazolation of tertiary amines was developed, affording the biologically valuable alkylated thiazoles via the aminomethylation of sulfonylthiazoles. The reaction is metal and oxidant free, with a broad substrate scope that tolerates both aliphatic and aromatic amines. The successful applications in the gram-scale reaction and late-stage functionalization of drug-like molecules in mild conditions under room temperature have qualified the protocol to be practical and cost-effective. [ABSTRACT FROM AUTHOR]