Asymmetric [4 + 3] Annulations for Constructing Divergent Oxepane Frameworks via Cooperative Tertiary Amine/Transition Metal Catalysis

We report asymmetric [4 + 3] annulations between isatin-derived Morita–Baylis–Hillman carbonates and two types of vinyl carbonates synergistically catalyzed by tertiary amines and transition metals, through chemoselective assemblies of in situ formed allylic ylides and metal-containing 1,4-dipoles. A range of oxepane frameworks are generally constructed in moderate to good yields with high stereocontrol. Moreover, all four diastereomers for the products bearing vicinal stereocenters are accessible by tuning tertiary amine and metal catalysts.