H-Terminated Catellani Strategy to Aryl β-Ethanol Enables Collective Total Syntheses of Pyranonaphthoquinone Natural Products.

We report an ipso-H-terminated variant using inexpensive formate as the terminating reagent. Coupling with diverse epoxides provides complementary access to valuable aryl β-ethanols with high regioselectivity. Integration with oxa-Pictet-Spengler and Ullmann reactions enables a collective total synthesis of pyranonaphthoquinone natural products. This strategy features significantly reduced synthetic steps, improved overall yields, and robust conditions, establishing a modular platform for structurally diverse aryl ethanol scaffolds and facilitating systematic bioactivity studies.