Asymmetric catalysis with short-chain peptides

• Enantioselective and diastereoselective synthesis of atropoisomers.
• Stereoselective synthesis of acyclic compounds bearing all-carbon quaternary stereogenic centers.
• Regioselective epoxidations, thiocarbonylations, acylations and phosphorylations of complex natural products.
• Tunable chemoselectivity and stereoselectivity of peptidic catalysts.
• Peptide catalysis in water — on the role of peptides in the chemical evolution of enzymes.

Within this review article we describe recent developments in asymmetric catalysis with peptides. Numerous peptides have been established in the past two decades that catalyze a wide variety of transformations with high stereoselectivities and yields, as well as broad substrate scope. We highlight here catalytically active peptides, which have addressed challenges that had thus far remained elusive in asymmetric catalysis: enantioselective synthesis of atropoisomers and quaternary stereogenic centers, regioselective transformations of polyfunctional substrates, chemoselective transformations, catalysis in-flow and reactions in aqueous environments.