The first synthesis of the ABC-ring system of 'upenamide.
The first synthetic route to the spirooxaquinolizidinone core (ABC core) of the macrocyclic marine alkaloid 'upenamide (1) has been developed. All five stereocenters were introduced with complete stereocontrol. The hydroxyl group at C-11 was introduced by a regio- and stereoselective SeO(2)-mediated allylic oxidation. The spirocyclic skeleton was formed by a stannous chloride induced deacetalization-bicyclization procedure. Further stereocenters were introduced by an enzymatic desymmetrization and by incorporation of an (S)-malic acid derived building block.
Schmidt
Jan Peter
JP
Department of Chemistry, University of York, York, YO10 5DD, U.K.
Beltrán-Rodil
Sandra
S
Cox
Rhona J
RJ
McAllister
Graeme D
GD
Reid
Mark
M
Taylor
Richard J K
RJ
D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D011807:Quinolizines / Q000138:chemical synthesis* / Q000737:chemistry; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D011807:Quinolizines; D013141:Spiro Compounds; C418125:upenamide