The behavior of different aromatic and heteroaromatic rings in a non-phenol
ic oxidative biaryl coupling process using PIFA [phenyliodine(III)bis(trifl
uoroacetate)] as the source of hypervalent iodine was studied. The experime
nts carried out led us to the construction of the basic skeletons of phenan
threne, naphthothiophene and pyrroloisoquinoline tricycles in a short and e
fficient way. The study was also extended to the preparation of phenanthroi
d-fused thiazoles.