Eight-Step Enantiodivergent Synthesis of (+)- and (-)-Lingzhiol.

An eight-step enantioselective synthesis of lingzhiol is described herein. The sense of an asymmetric Michael reaction is reversed by the choice of metal source, enabling facile access to both enantiomers. A spontaneous semipinacol ring contraction enables mild construction of the lingzhiol core, and radical-mediated benzylic oxidation proceeds in the presence of an unprotected secondary alcohol. This represents the shortest enantioselective synthesis of lingzhiol to date and the only enantiodivergent approach to both enantiomers of this meroterpenoid natural product.