title: Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement.
abstract: The highly diastereoselective base-promoted intramolecular cyclization of a variety of enantiopure sulfinyl dienyl amines provides novel sulfinyl tetrahydropyridines that are readily converted to 3-hydroxy tetrahydropyridines via sigmatropic rearrangement. The influence of N- and C- substituents on the process has been studied. Procedures to shorten the sequence such as the tandem cyclization followed by [2,3]-sigmatropic rearrangement, as well as cyclization of the free amine, under Boc- or ArSO- deprotection conditions have been examined. Good to excellent levels of selectivity are generally observed for the reported transformations (dr: 75/25 to >98/2). A novel protocol to access substituted amino dienyl sulfoxides is also reported.
authors.affiliation: †Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Carmen
authors.initials: C
authors.lastname: Simal
authors.affiliation: †Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Robert H
authors.initials: RH
authors.lastname: Bates
authors.affiliation: †Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Mercedes
authors.initials: M
authors.lastname: Ureña
authors.affiliation: †Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Irene
authors.initials: I
authors.lastname: Giménez
authors.affiliation: †Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Christina
authors.initials: C
authors.lastname: Koutsou
authors.affiliation: ‡Instituto de Química Física Rocasolano, IQFR-CSIC, Serrano 119, 28006 Madrid, Spain.
authors.forename: Lourdes
authors.initials: L
authors.lastname: Infantes
authors.affiliation: †Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Roberto
authors.initials: R
authors.lastname: Fernández de la Pradilla
authors.affiliation: †Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Alma
authors.initials: A
authors.lastname: Viso
mesh_terms: D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D015394:Molecular Structure; D010880:Piperidines / Q000138:chemical synthesis*; D013237:Stereoisomerism; D013454:Sulfoxides / Q000737:chemistry*
chemical_list: D000588:Amines; D010880:Piperidines; D013454:Sulfoxides; C062320:N-hydroxypiperidine