Diastereoselective Synthesis of Macrocyclic Spiro and Dispiro‐1,4‐dithianes, ‐1,4‐oxathianes, and ‐1,4‐dithiepanes through Intramolecular Sulfonium Ylides

Abstract

AbstractThe synthesis of functionalized C2‐symmetric as well as unsymmetrical macrocyclic spiro and dispiro‐1,4‐dithianes, ‐1,4‐oxathianes, and 1,4‐dithiepanes was achieved in a highly diastereoselective manner from the reactions of thiol‐protected cyclic and acyclic diazocarbonyl compounds in the presence of a rhodium(II) acetate dimer catalyst at room temperature. These macrocyclic compounds were obtained by the formation of 9‐ to 13‐membered intramolecular sulfonium ylides followed by a Stevens rearrangement.