We report a novel and general method to access a highly under‐studied privileged scaffold—pyrimidines bearing a trifluoroborate at C4, and highlight the broad utility of these intermediates in a rich array of downstream functionalization reactions. This chemistry is underpinned by the unique features of the trifluoroborate group; its robustness provides an opportunity to carry out chemoselective reactions at other positions on the pyrimidine while providing a pathway for elaboration at the C−B bond when suitably activated.

The synthesis of perfluoroalkyl-substituted (hetero)arenes by benzannulation strategies is complementary to ring functionalization approaches as it obviates the need for pre-existing functionality and innate regiocontrol. We report a mild and regiospecific boron-directed benzannulation method as a vehicle for accessing a range of perfluoroalkyl-substituted (hetero)aromatic building blocks that can be readily elaborated through established C–B bond functionalization processes.

We report a novel and general method to access a highly under‐studied privileged scaffold—pyrimidines bearing a trifluoroborate at C4, and highlight the broad utility of these intermediates in a rich array of downstream functionalization reactions. This chemistry is underpinned by the unique features of the trifluoroborate group; its robustness provides an opportunity to carry out chemoselective reactions at other positions on the pyrimidine while providing a pathway for elaboration at the C−B bond when suitably activated.