Catalytic Three-Component Synthesis of Functionalized Naphtho[2,1-b]oxecines via a Double Bond Cleavage–Rearrangement Cascade

Cheng-Long Ji, Wen-Juan Hao,* Jie Zhang, Fang-Zhou Geng, Ting Xu, Shu-Jiang Tu,* Bo Jiang*

A new double annulation cascade involving [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) process was first reported, leading to the generation of unprecedented dibenzoannulated naphtho[2,1-b]oxecines with good to ex.cellent yields and high stereoselectivity through catalytic scission/recombination of C–C double bonds under the mild conditions. Y(OTf)₃-Catalyzed three-component reaction of α-alkynyl naphthalen-2-ols with β,γ-unsaturated α-ketoesters enabled direct ring expansion of naphthalene ring and carbon-carbon double bond cleavage/ rearrangement of α-ketoesters to give macrocyclic architectures.

Org. Lett. 2019, 21, 6494-6498