title: Asymmetric synthesis of N,O,O,O-tetra-acetyl d-lyxo-phytosphingosine, jaspine B (pachastrissamine), 2-epi-jaspine B, and deoxoprosophylline via lithium amide conjugate addition.
abstract: The highly diastereoselective anti-aminohydroxylation of (E)-gamma-tri-iso-propylsilyloxy-alpha,beta-unsaturated esters, via conjugate addition of lithium (S)-N-benzyl-N-(alpha-methylbenzyl)amide and subsequent in situ enolate oxidation with (+)-(camphorsulfonyl)oxaziridine, has been used as the key step in the asymmetric synthesis of N,O,O,O-tetra-acetyl d-lyxo-phytosphingosine (20% yield over 7 steps), the anhydrophytosphingosine jaspine B (10% yield over 9 steps), 2-epi-jaspine B (14% yield over 9 steps), and the Prosopis alkaloid deoxoprosophylline (26% yield over 7 steps).
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, UKOX1 3TA.
authors.forename: Elin
authors.initials: E
authors.lastname: Abraham
authors.forename: E Anne
authors.initials: EA
authors.lastname: Brock
authors.forename: José I
authors.initials: JI
authors.lastname: Candela-Lena
authors.forename: Stephen G
authors.initials: SG
authors.lastname: Davies
authors.forename: Matthew
authors.initials: M
authors.lastname: Georgiou
authors.forename: Rebecca L
authors.initials: RL
authors.lastname: Nicholson
authors.forename: James H
authors.initials: JH
authors.lastname: Perkins
authors.forename: Paul M
authors.initials: PM
authors.lastname: Roberts
authors.forename: Angela J
authors.initials: AJ
authors.lastname: Russell
authors.forename: Elena M
authors.initials: EM
authors.lastname: Sánchez-Fernández
authors.forename: Philip M
authors.initials: PM
authors.lastname: Scott
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Smith
authors.forename: James E
authors.initials: JE
authors.lastname: Thomson
mesh_terms: D000577:Amides / Q000737:chemistry*; D001596:Benzylamines / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry; D013110:Sphingosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C530277:2-hydroxymethyl-6-dodecylpiperidin-3-ol; D000577:Amides; D001596:Benzylamines; D009942:Organometallic Compounds; D010880:Piperidines; C468594:pachastrissamine; C520613:tetraacetyl-phytosphingosine; D008094:Lithium; D013110:Sphingosine