This investigation presents an innovative methodology for the direct deoxygenative alkenylation of ketones, utilizing pinacolborane as the reducing agent in the presence of B(C 6F 5) 3 catalyst. A series of aryl ketones containing different functional groups such as hydroxyl, amino, alkynyl, vinyl, and ester groups were found to be well-tolerated. This transformation has also been nicely applied to the gram-scale late-stage functionalization of pharmacologically significant compounds sertraline and conivaptan. Comprehensive mechanistic investigations have elucidated a plausible reaction pathway that proceeds through sequential carbonyl hydroboration, deboration, and deprotonation processes.