<jats:p>From the endemic Cuban species <jats:italic>Rauvolfia salicifolia</jats:italic> GRISEB nine alkaloids were isolated of which the following seven had been already described: (+)-ajmalidine (<jats:italic>I</jats:italic>), (-)-reserpiline (<jats:italic>II</jats:italic>), (-)-isoreserpiline (<jats:italic>III</jats:italic>), (-)-isocarapanaubine (<jats:italic>IV</jats:italic>), (-)-ajmalicine (<jats:italic>V</jats:italic>), (+)-vellosimine (<jats:italic>VI</jats:italic>), and (+)-yohimbine (<jats:italic>VII</jats:italic>). The structure of (-)-raucubaine (<jats:italic>VIII</jats:italic>) had been previously determined by X-ray diffraction and the structure of the alkaloid (-)-raucubainine (<jats:italic>IX</jats:italic>) was suggested on the basis of its conversion to (-)-raucubaine (<jats:italic>VIII</jats:italic>). The absolute configuration of (-)-raucubaine and (-)-raucubainine was elucidated by CD spectroscopy.