One-Pot Unsymmetrical {[4 + 2] and [4 + 2]} Double Annulations of o/o′-C–H Bonds of Arenes: Access to Unusual Pyranoisoquinolines

With the aid of a transformable sulfoximine directing group, unprecedented one-pot unsymmetrical double annulations {[4 + 2] and [4 + 2]} of hetero(arenes) with alkynes are revealed under Ru(II) catalysis. Functionalization of both ortho-C–H bonds of (hetero)arene is reflected in the building of unusual 6,6-fused pyranoisoquinoline skeletons. Construction of four [(C–C)–(C–N) and (C–C)–(C–O)] bonds occurs in one step under single catalytic conditions. The challenging unsymmetrical double annulations of both o-C–H bonds of arenes with two distinct alkynes is effectively demonstrated. Control experiments and deuterium scrambling findings are shown.