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.
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).
Abraham
Elin
E
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, UKOX1 3TA.
Brock
E Anne
EA
Candela-Lena
José I
JI
Davies
Stephen G
SG
Georgiou
Matthew
M
Nicholson
Rebecca L
RL
Perkins
James H
JH
Roberts
Paul M
PM
Russell
Angela J
AJ
Sánchez-Fernández
Elena M
EM
Scott
Philip M
PM
Smith
Andrew D
AD
Thomson
James E
JE
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
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