title: Stereoselective reaction of 2-carboxythioesters-1,3-dithiane with nitroalkenes: an organocatalytic strategy for the asymmetric addition of a glyoxylate anion equivalent.
abstract: An efficient organocatalytic methodology has been developed to perform the stereoselective addition of 2-carboxythioesters-1,3-dithiane to nitroalkenes. Under mild reaction conditions γ-nitro-β-aryl-α-keto esters with up to 92% ee were obtained, realizing a formal catalytic stereoselective conjugate addition of the glyoxylate anion synthon. The reaction products are versatile starting materials for further synthetic transformations; for example, the simultaneous reduction of the nitro group and removal of the dithiane ring was accomplished, allowing the preparation of a GABAB receptor agonist baclofen.
authors.affiliation: Dipartimento di Chimica, Universita' degli Studi di Milano, via Golgi 19, I-20133 Milano, Italy. maurizio.benaglia@unimi.it.
authors.forename: Elisabetta
authors.initials: E
authors.lastname: Massolo
authors.forename: Maurizio
authors.initials: M
authors.lastname: Benaglia
authors.forename: Andrea
authors.initials: A
authors.lastname: Genoni
authors.forename: Rita
authors.initials: R
authors.lastname: Annunziata
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Celentano
authors.forename: Nicoletta
authors.initials: N
authors.lastname: Gaggero
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000838:Anions / Q000737:chemistry*; D001418:Baclofen / Q000494:pharmacology*; D002384:Catalysis; D058786:GABA-B Receptor Agonists / Q000494:pharmacology*; D006038:Glyoxylates / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry*; D018080:Receptors, GABA-B / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D000838:Anions; D058786:GABA-B Receptor Agonists; D006038:Glyoxylates; D006571:Heterocyclic Compounds; D009574:Nitro Compounds; D018080:Receptors, GABA-B; C012947:1,3-dithiane; D001418:Baclofen