Ligand-Controlled Iron-Catalyzed Coupling of α-Substituted β-Ketoesters with Phenols

A chemo-, regio-, and stereoselective FeCl3/1,10-phenanthroline-catalyzed cross dehydrogenative coupling (CDC) reaction between phenols and alpha-substituted beta-ketoesters was developed. The reaction creates a new quaternary carbon center within a polycyclic hemiacetal or polycyclic spirolactone architecture. The applicability of the new method to the synthesis of natural products was demonstrated by a possible biomimetic synthesis of the lachnanthospirone core.