Baruol ( 1 ) and Leonal ( 2 ), first examples of tetracyclic triterpenes possessing a D: B-friedobaccharane skeleton, were isolated from Maytenus blepharodes and M. chiapensis, respectively. Their structures were established by spectroscopic analysis, molecular modeling studies and biogenetic background. The implication of the D: B-friedobaccharenyl cation in the biosynthetic route of baccharane and shionane skeletons is discussed. Baruol exhibited β-glucuronidase inhibitory activity, a target in the search for hepatoprotective agents.