Nucleophilic substitution of carbon-leaving groups (CLGs) and base-catalyzed alcohol dehydration reactions are rare in the organic chemistry literature. Herein, we introduce an unprecedented example of a novel reaction that challenges the poor leaving group abilities of both CLGs and hydroxide ions via a concerted transition state, demonstrating E1cB_anion step-2/S_NAcyl step-1 reaction mechanism interference, displayed by S1 and S2 scaffolds in an alkaline medium (Schemes 5,8). The work offers swift access to C–C bond hydrolysis in the form of ketone α-hydrolytic cleavage under environmentally convenient conditions. Three reaction products were characterized by single-crystal X-ray crystallography, which supported their computed most stable ring conformer structures. Experimental and DFT evidence evoke fast reaction rates (TS1′, ΔG^‡ = 26.8 kcal/mol, Scheme 5 and TS5b, ΔG^‡ = 14.9 kcal/mol …