A one-pot, telescopic procedure to directly convert the (hetero)cyclohexylidenemalononitriles into bis-trifluoromethylated (hetero)cyclohexane-4-carboxylic acids was finally studied (Figure ). The conditions developed involve the standard protocol for bis-trifluoromethylation/reduction. After an aqueous work-up, the crude material was found to be readily converted to carboxylic acids 6a -6c by treatment with hydrogen peroxide (H2O2) in acetonitrile under basic conditions. The thiopyran substrate 3c underwent additional oxidation into the sulfone 6a. These conditions allow for direct access to bis-trifluoromethylated, physicochemically-altered, analogs of Amenamevir, Maraviroc, Velneperit or Cadazolid cores. The bis-trifluoromethylated carboxylic acids were obtained with high diastereomeric ratios (>20:1) with yields ranging from 52% -65% over the telescoped sequence (Figure .i.). Notably, the piperidine substrate still converted into the a-hydroxylation product 6d. This unusual chemoselectivity is not well understood at present. DFT calculations support that the trans diastereomer of the bis-trifluoromethylated compound is thermodynamically favored over the cis-diastereomer (-1.64 kcal/mol) (Figure .ii.). Deprotonation of cis-and trans-diastereomers show a barrier of 4.7 and 6.6 kcal/mol, respectively, with a Keq of 3.28 -4 .