AbstractFrom the leaves of the African ApocynaceaPleiocarpa talbotii Wernhama novel indole alkaloid, talbotine, C21H24N2O4, has been isolated. Talbotine (1) contains a secondary N(b)‐atom and a cyclic hemiacetal group. Catalytic hydrogenation leads to 19, 20‐dihydrotalbotine (6), hydrogenation in the presence of formaldehyde gives N(b)‐methyl‐19, 20‐dihydrotalbotine (8). In the presence of sodium methoxide and methanol,1is converted into the lactone12and the methyl ester13. In these reactions carbon 17 is lost as formic acid. These data, together with the analyses of the NMR. spectra of talbotine and its derivatives as well as the interpretation of the various types of the mass spectral fragmentation, lead to formula1for the alkaloid.Dehydrogenation of talbotine methyl ether (3) with palladium and maleic acid gives the ß‐carboline derivative26. The N(b)‐methiodide of the latter is converted into N(b)‐methyl‐talbotine methyl ether on reduction with sodium borohydride. From these data as well as from the analyses of NMR. and IR. spectra the complete relative stereochemistry of talbotine could be derived. Application of theHoreaumethod to the nitrogen atom b of the methyl ether3on the one hand and to the hydroxyl group on C17 in N(b)‐methyl‐19, 20‐dihydrotalbotine (8) on the other hand gives consistent results and establishesSco