Pd-catalyzed enantioselective aerobic oxidation of secondary alcohols: Applications to the total synthesis of alkaloids

Enantioselective syntheses of the alkaloids (-)-aurantioclavine, (+)-amurensinine, (-)-lobeline, and (-)- and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility of an aryne C-C insertion reaction in accessing complex polycyclic frameworks is also described. ; © 2008 American Chemical Society. Received June 20, 2008. The authors thank the NIH-NIGMS (R01 GM65961-01), California TRDRP (postdoctoral fellowships to Y.K.R. and S.K., and predoctoral fellowship to J.T.B.), NDSEG (predoctoral fellowships to D.C.E. and U.K.T.), NSF (predoctoral fellowship to D.C.E.), Caltech, AstraZeneca, Boehringer Ingelheim, Johnson & Johnson, Pfizer, Merck, Amgen, Abbott, Research Corporation, Roche, and GlaxoSmithKline for generous funding ; Accepted Version - nihms-69334.pdf