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

Key Points

• The aim is to develop a method for constructing fused polycycles using Pd-catalyzed geminal coupling.
• Utilized Pd-catalyzed geminal heterocoupling to forge fused tricyclic cores.
• Performed mechanistic studies to explore the autotandem pathway.
• Target-oriented elaboration to advance synthetic intermediates.
• Successfully generated fused 6/5/6 polycycles, essential for natural product synthesis.
• Mechanistic evidence supports an autotandem pathway involving initial cross-coupling followed by oxidative cyclometalation.