title: Stereoselective metal-free synthesis of β-amino thioesters with tertiary and quaternary stereogenic centers.
abstract: β-Amino thioesters are important natural building blocks for the synthesis of numerous bioactive molecules. An organocatalyzed Mannich reaction was developed which provides direct and highly stereoselective access to acyclic β(2)- and β(2,3,3)-amino thioesters with adjacent tertiary and quaternary stereocenters. Mechanistic studies showed that the stereochemical course of the reaction can be controlled by the choice of the substrates. The β-amino thioesters were further functionalized by, for example, stereoselective decarboxylation to access β(2,3)-frameworks. In addition, the value of the β-amino thioesters was shown in coupling-reagent-free peptide synthesis.
authors.affiliation: ETH Zürich, Laboratorium für Organische Chemie, D-CHAB, Wolfgang Pauli-Strasse 10, 8093 Zürich (Switzerland) http://www.wennemers.ethz.ch.
authors.forename: Annette
authors.initials: A
authors.lastname: Bahlinger
authors.forename: Sven P
authors.initials: SP
authors.lastname: Fritz
authors.forename: Helma
authors.initials: H
authors.lastname: Wennemers
mesh_terms: D000596:Amino Acids / Q000737:chemistry; D002384:Catalysis; D002930:Cinchona Alkaloids / Q000737:chemistry; D018360:Crystallography, X-Ray; D003653:Decarboxylation; D004952:Esters; D008670:Metals / Q000737:chemistry; D008968:Molecular Conformation; D010455:Peptides / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013457:Sulfur Compounds / Q000737:chemistry*
chemical_list: D000596:Amino Acids; D002930:Cinchona Alkaloids; D004952:Esters; D008670:Metals; D010455:Peptides; D013457:Sulfur Compounds
keywords: cinchona alkaloids; organocatalysis; peptide coupling; thioesters; β-amino acid