Dual-Pathway Skeletal Editing of Isoquinolines

A dual-pathway skeletal editing of isoquinolines was described. A common Tf 2 O-activated intermediate reacts with secondary amines and can be selectively directed under orthogonal conditions. Blue-light irradiation enables N-to-C transmutation to form naphthalenes, whereas microwave heating promotes cascade skeletal editing/annulation to yield benzo[ f ]quinazolines. Acetonitrile acts as a bifunctional C1 synthon, enabling stepwise N-to-C and C-to-C transformations, providing a rare route to benzo[ f ]quinazolines.