Total synthesis of (-)-penicimutanin a and related congeners.

The first total synthesis of penicimutanin A () was achieved within 10 steps (LLS). Key innovations in this synthesis consist of (1) a highly efficient electro-oxidative dearomatization; (2) an unprecedented bisoxirane-directed intermolecular aldol reaction from the sterically hindered face of the ketone and (3) the diastereoselective one-step Meerwein-Eschenmoser-Claisen rearrangement enabling the construction of vicinal quaternary stereocenters. Related family members penicimutanolone () and penicimutatin () have also been synthesized alongside, elucidating their absolute configurations, hence the absolute configuration of .