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Steroidal epoxides are smoothly cleaved by hydrogen cyanide-triethylaluminium and by diethylaluminium cyanide under mild conditions to give the corresponding trans-diaxial p-cyanohydrins, except for the 5p,l OP-epoxide (XXVIb) which gives the cis-p-cyanohydrin (XXVIII) as well as the major, trans-diaxial product (XXVIIb). The compounds examined included the 5a,6a-, 5p,6p-, 9cr.11 a-, 9p.11 p-, 16a,17a-, 2a,3cr-, 3cr,4u-, 11 a,l2a-, 5a,l Oa-, and 58.1 Op-epoxides. The successful cleavage of the 9a,l1 a-epoxide (VIII) to give the Sa-hydroxy-11 9-cyano-steroid (IX) is significant in view of the fact that 9a,l 1 a-epoxides are known to resist cleavage by lithium aluminium hydride or hydrogen halides. 9-Cyanohydrins are also obtained from the corresponding B-bromohydrins by treatment with hydrogen cyanide and triethylaluminium.

* Calculated by subtracting the absorption of unsaturated lactone ring at 218 mil from the U. V. of III, 1~~-{ 221 mil (log e 4.36). ** Formamide•acetone (1: 4) mixture was used as the stationary phase for these mobile phases.