The bis-trifluoromethylation and 1,2,3-all-cis-stereochemical outcomes can be rationalized as described in Figure . It is proposed that the in situ, base-generated alkylidenemalononitrile anion [Int-I] reacts with Togni's reagent in "runaway" fashion. This is suggested because the monotrifluoromethyl group was largely not observed during optimization. It is proposed that an inductive effect due to the initial trifluoromethylation yields the mono-trifluoromethyl cycloalkylidenemalononitrile more acidic than 1, thus influencing the efficiency of reaction towards bis-trifluoromethylation. Regarding stereochemistry, it is proposed that iterative axial trifluoromethylation occurs to [Int-II-ax] and that the 1,3-diaxial conformer is favored energetically. At first glance, this is somewhat confounding considering that cis-1,3-diaxial-dimethylcyclohexane has a +5.6 kcal/mol higher energy than the diequatorial conformer. However, gamma-substituted cycloalkylidenemalononitriles prefer axial orientation of substituents to relieve 1,3-allylic (A 1,3 ) strain and due to orbital interactions. Supporting this, DFT calculations found that the diaxial-bis-trifluoromethyl conformer [Int-II-ax] is the ground state conformer in this case (Figure .ii.). For the computational analysis, two different substrates were examined. The N-Ts substrate yielded two near-isoenergetic ground state structures, a chair and a boat. The boat structure is uniquely tied to a neighboring group p-p* interaction between the Ts-and alkylidenemalononitrile group. As such, the "CH2" substrate yielded only one major ground state structure: a chair conformation with both CF3 groups axial. As a final point, continued trifluoromethylation (beyond bis-trifluoromethylation) may not be observed because the cis-diaxial conformer [Int-B-ax] is not acidic and therefore cannot continue to react beyond bis-trifluoromethylation; the gamma-C-Hs are not properly aligned with the alkylidenemalononitrile p-system to be acidic/deprotonated. Upon addition of NaBH4, hydride is delivered axially (equatorial is "blocked" by the trans-diaxial trifluoromethyl groups) to the alkylidenemalononitrile functional group. Chair-chair interconversion from 3a-ax produces the conformer 3a-eq, observed by X-ray crystallography. Further, this conformer is consistent with the lowest energy conformer determined by DFT calculations.