First enantioselective total synthesis of (-)-Centrolobine.
[structure: see text] The first enantioselective total synthesis of (-)-Centrolobine is described. The key reaction is the synthesis of the cis-disubstituted tetrahydropyran framework by intramolecular cyclization of the enantiopure hydroxyketone 3 with Et3SiH and TMSOTf. The stereoselective reduction of the beta-ketosulfoxide 4 is the source of chirality. Revision of the absolute configuration of (-)-Centrolobine is proposed.
Colobert
Françoise
F
Laboratoire de Stéréochimie associé au CNRS, Université Louis Pasteur, E.C.P.M., 25 rue Becquerel 67087 Strasbourg Cedex 2, France. fcolober@chimie.u-strasbg.fr
Mazery
Renaud Des
RD
Solladié
Guy
G
Carreño
M Carmen
MC
D000447:Aldehydes; D003500:Cyclization; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D010946:Plants, Medicinal; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D013454:Sulfoxides / Q000737:chemistry*
D000447:Aldehydes; D007202:Indicators and Reagents; D011714:Pyrans; D013454:Sulfoxides; C432457:centrolobin