An investigation of the reaction of catharanthine with zinc in glacial acetic acid is presented. Four isomeric carbomethoxydihydrocleavamine derivatives have been isolated and fully characterized. It is also shown that heating catharanthine in a mixture of acetic acid and sodium borohydride provides a very convenient method for the preparation of the previously unknown 18β-carbomethoxycleavamine. These compounds provide the desired intermediates for the synthesis of various Iboga alkaloids. © 1970, American Chemical Society. All rights reserved.