The indole alkaloid, raumacline, is biosynthesized from ajmaline, when the latter was fed to cell suspensions of Rauwolfia serpentina. Formation in catalysed by two enzymes, a cell wall-bound peroxidase followed by a NADPH2-dependent reductase. The first enzyme cleaves ajmaline oxidatively leading to a C-21 epimeric mixture of 21-hydroxyraumacline, a novel alkaloid, which, in turn, is reduced under formation of raumacline. The peroxidase reaction is not specific for Rauwolfia cells whereas the reductase is present exclusively in Rauwolfia cell suspensions. The reductase has been purified to homogeneity. The enzyme is highly substrate specific, only accepting 21-hydroxyraumacline and perakine, the latter leading to raucaffrinoline by reduction. © 1995.