Solvent-Controlled Divergent Catalysis toward the Synthesis of Fluvastatin Analogs.

A solvent-controlled, divergent Rh(III)-catalyzed strategy enables the synthesis of structurally diverse fluvastatin analogs. Enantioenriched α,β-unsaturated ketones derived from 2-deoxy-d-ribose undergo selective C2-H functionalization of indoles, affording olefination or hydroarylation products under complementary conditions. The method shows broad scope and functional group tolerance. Mechanistic studies indicate a solvent-driven switch between β-hydride elimination and protodemetalation, providing rapid access to both enantiomeric series of fluvastatin-inspired scaffolds.