Preparations of SF5- and CF3-substituted arenes utilizing the 7-oxabicyclo[2.2.1]hept-2-ene synthonesElectronic supplementary information (ESI) available: Copies of 1H, 13C, 19F NMR, and 2D spectra of synthesized products, X-ray structures of 8, 10a, 14c. CCDC 951078-951080. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3ob41560k

The synthesis of SF 5 - and CF 3 -substituted benzenes and naphthalenes from various 7-oxanorbornene derivatives utilizing SF 5 Cl and CF 3 I radical addition reactions, followed by dehydrohalogenation and aromatization, is reported. The differences in the behavior of the SF 5 - and CF 3 -containing intermediates under basic and acidic conditions are discussed. The experimentally observed high regioselectivities of the formation of 2-R F -substituted-1-naphthols agree well with the ab initio computations, revealing the first example of the SF 5 HO hydrogen bonding. The synthesis of SF 5 - and CF 3 -substituted benzenes and naphthalenes from various 7-oxanorbornene derivatives utilizing SF 5 Cl and CF 3 I radical addition reactions, followed by dehydrohalogenation and aromatization, is reported.