Site-selective radical reactions of kinetically stable open-shell singlet diradicaloid difluorenoheteroles with tributyltin hydride and azo-based radical initiators.

We have demonstrated site-selective radical reactions of the kinetically stable open-shell singlet diradicaloids difluoreno[3,4- b :4',3'- d ]thiophene (DFTh) and difluoreno[3,4- b :4',3'- d ]furan (DFFu) with tributyltin hydride (HSn( n -Bu) 3 ) and azo-based radical initiators. Treatment of these diradicaloids with HSn( n -Bu) 3 induces hydrogenation at the ipso -carbon in the five-membered rings, while treatment with 2,2'-azobis(isobutyronitrile) (AIBN) induces substitution at the carbon atoms in the peripheral six-membered rings. We have also developed one-pot substitution/hydrogenation reactions of DFTh/DFFu with various azo-based radical initiators and HSn( n -Bu) 3 . The resulting products can be converted into substituted DFTh/DFFu derivatives via dehydrogenation. Theoretical calculations unveiled a detailed mechanism of the radical reactions of DFTh/DFFu with HSn( n -Bu) 3 and with AIBN, and that the site-selectivity of these radical reactions is controlled by the balance of the spin density and the steric hindrance in DFTh/DFFu.