Pd(II)-Mediated Alkynediol Spiroketalization: First Total Synthesis of (−)-Cephalosporolide E and (+)-Cephalosporolide F

Herein we describe a concise assembly of the central 1,6-dioxaspiro[4.4]nonane core of cephalosporolides E/F by employing a Pd-mediated alkynediol cycloisomerization and their total synthesis. On the basis of spectroscopic data and optical rotation values, the absolute configurations of cephalosporolides E/F were proposed.