Unstrained C–C bond activation and directed fluorination through photocatalytically-generated radical cations† †Electronic supplementary information (ESI) available: NMR spectra and computational data. See DOI: 10.1039/c5sc01973g Click here for additional data file.

General: [S:2] Representative procedures: [S:3] Characterization data: 6-fluoro-6-phenyl-hexanoic acid (1): [S:4, S:10-S:12] methyl 6-fluoro-6-phenylhexanoate (2): [S:4, S:13-S:15] 6-fluoro-6-phenylhexan-1-ol (3): [S:4, S:16-S:18] 6-fluoro-6-(p-tolyl)hexanoic acid (4): [S:5, S:19-S:21] 6-(4-(tert-butyl)phenyl)-6-fluorohexanoic acid (5): [S:5, S:22-S:24] 6-fluoro-6-(4-fluoro)phenyl-hexanoic acid (6): [S:5, S:25-S:27] 6-(4-chlorophenyl)-6-fluorohexanoic acid (7): [S:6, S:28-S:30] 6-(2-bromophenyl)-6-fluorohexanoic acid (8): [S:6, S:31-S:33] 6-fluoro-6-(naphthalen-1-yl)hexanoic acid (9): [S:6, S:34-S:36] 6-fluoro-6-(4-(2-phenyl-1,3-dioxolan-2-yl)phenyl)hexanoic acid (10): [S:7, S:37-S:39] 6-(4-acetylphenyl)-6-fluorohexanoic acid (11): [S:7, S:40-S:42] 2-(3-fluoro-3-phenylpropyl)benzoic acid (12): [S:7, S:43-S:45] cis-2-(3-fluoro-3-phenylpropyl)cyclohexane-1-carboxylic acid (13): [S:8, S:46-S:48] 6-fluoro-2,6-diphenylhexanoic acid (14): [S:8, S:49-S:51] 6-fluoro-1,6-diphenyl-hexanone (15): [S:8, S:52-S:54] 5-fluoro-5-phenylpentanoic acid (17): [S:9, S:55-S:57] 7-fluoro-7-phenylheptanoic acid (18): [S:9, S:58-S:60] 8-fluoro-8-phenyloctanoic acid (19): [S:9, S:61-S:63] 12-fluoro-12-phenyldodecanoic acid (20): [S:9, S:64-S:66] Intermolecular Competition Experiments: [S:67-S:69] Computational Data: [S:70-S:79] Table of calculated C-C bond lengths in radical cation geometries: [S:80]