Collective Synthesis of Furanocoumarin Natural Products through a Radical‐mediated Construction of Furanocoumarin Skeletons

Abstract Furanocoumarins are attractive targets in the synthetic organic and medicinal chemistry field because of their structural diversity and interesting biological properties. Herein, we describe the synthesis of furanocoumarin natural products from common furanocoumarin skeletons. A key step was a novel intramolecular radical cyclization onto nitrile to synthesize angular and linear franocoumarins, which was optimized by reacting iodocoumarin derivatives in the presence of (Me 3 Si) 3 SiH and oxygen. These compounds served as intermediates in the syntheses of vaginidiol, vaginidin, oroselol, multivittan D, gaudichaudine, oreoselone, peucedanin, and smyrindiol, successfully demonstrating the versatility of the intermediates and utility of the radical cyclization method for accessing furanocoumarin natural products.