An improved synthetic approach to protopines based on the sequential Hofmann elimination, hydroboration and oxidation of N-(arylmethyl)berbinium salts has been designed. By using berberine chloride as the starting material, this sequence of reactions has provided two new nonnatural protopines, N-benzyl-N-nordihydroallocriptopine and N-(p-methoxybenzyl)-N- nordihydroallocriptopine and the natural allocriptopine. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.