Pd-Catalyzed Geminal Coupling for the Construction of Fused Polycycles and Natural Product Synthesis

methyl ester and xiamycin E, where the geminal heterocoupling forges the fused tricyclic core and provides advanced intermediates for subsequent target-oriented elaboration. Mechanistic studies support an autotandem pathway involving initial cross-coupling followed by oxidative cyclometalation. Collectively, these studies establish a useful method for the modular construction of fused 6/5/6 polycycles.