Entry [b] Variation from the standard conditions Yield (%) [c] With the optimized reaction conditions in hand, we then explored the reactivity of α-trifluoromethyl alkenes with different functionalities. With respect to α-trifluoromethyl styrenes, a diverse set of functionalities on the phenyl ring including phenyl (4aa), methyl (4ab), methoxy (4ac-ae), benzyloxy (4af, 4ag), chloro (4ah), cyano (4ai), and methylmercapto (4aj) were tolerated by the reaction with 1-cyclohexylethan-1-one derived dihydroquinazolinone 2a, thus giving rise to the expected cyclohexyl substituted gem-difluoroalkenes 4aa-4aj in moderate to high yields (38-93%). It is worth noting that for substrates containing a strong electron-deficient group at the para position of the phenyl ring, the hydroalkylation pathway pre-vailed over the defluoroalkylation to forge the trifluoromethylated compounds as the major product for aldehyde group (5ak:4ak = 10:1, 78% yield) or as a single product for cyano group (5al, 53% yield), which is consistent with our previous report. 18k, 18l Multiple polycycles and heterocycles including Scheme 3. Substrate Scope of Ketone-Derived Dihydroquinazolinone 2. [a] efficiencies of this reaction, and substrates with an ortho-substituent resulted in significantly decreased yields (4ae vs 4ac, 4am vs 4an). Gratifyingly, substrates derived from natural products and bioactive molecules, such as estrone (4aq) and isoxepac derivatives (4ar) could be successfully alkylated under our optimized conditions, further highlighting the synthetic utilities of this approach.