Herein we report on the development of a novel and efficient approach to the restriction of the conformational mobility of calix [6]arenes. The method involves the addition of tertiary alcohols to calix[6]arenes with one, three and six cyanomethoxy groups attached to the lower rim under modified Ritter reaction conditions. Alkylation of monocyanomethoxy-p-tertbutylcalix[6]arene (1) and 37,39,41-trimethoxy-38,40,42-tricyanomethoxy-p-tert-butylcalix[6]arene (2) with 3-R-1-adamantanols (R = H, CH 2 COOH) in trifluoroacetic acid afforded the corresponding mono-and triamides with conelike conformations. The partial alkylation of hexanitrile de-