Regiodivergent C–N Coupling of Quinazolinones Controlled by the Dipole Moments of Tautomers

Herein, we report that the dipole moments of tautomers can be the controlling factor for regiodivergent synthesis of either 14H-quinazolino[3,2-f]phenanthridin-14-ones or 6H-quinazolino[1,2-f]phenanthridin-6-ones, selectively, from unmasked 2-([1,1′-biphenyl]-2-yl)quinazolin-4(3H)-one. An intramolecular C(sp2)–NH coupling reaction mediated by PhI(OCOOCF3)2 could lead to two different regioisomers selectively at different temperatures when the dielectric constants of solvents like hexafluoroisopropanol and trifluoroacetic acid matched with the tautomer's dipole moments.