A sustainable photocatalytic approach has been established for trifluoroalkylation of isoquinoline via a three-component Minisci-type reaction using a green solvent. The polarity reversal radical cascade strategy renders the selective addition of an electrophilic CF radical to an olefin to forge a nucleophilic -centered radical. This multicomponent approach is operationally simple and environmentally benign with various functional groups, viz. aldehydes, acetals, amides, and halides. Mechanistic investigations were carried out to elaborate the reductive quenching catalytic pathway.
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