Enantioselective Synthesis of Cephalimysins B and C

The first synthesis of cephalimysins B and C is reported. The route features a Ni­(II)–diamine-catalyzed enantioselective conjugate addition of a densely substituted 3­(2H)-furanone and an efficient dihydroxylation–lactonization sequence as key steps in the assembly of the spirocyclic core. The fully synthetic strategy is amenable to analog preparation.