significantly impact this reaction, and ortho-substituted substrates also reviewed good reactivity and chemo-selectivity (3w and 3y). Encouragingly, polycyclic naphthalene (3e', 3f') and heterocyclic dibenzothiophene (3g', 3h') were also compatible with this transformation. To further showcase the synthetic utility of this β-scission/gem-difluoroallylation reaction, we then probed the feasibility of late-stage functionalization (LSF) of several natural products and bioactive drug molecules, such as D-ribose, D(+)-glucose, Gemfibrozil, Sclareolide, and Benzocaine. In all cases, the desired gem-difluoroalkenes 3i'-m' were achieved with good chemo-selectivity (8:1 ->99:1). Next, we turned our attention to the substrate scope for the synthesis of trifluoroalkanes 4. As shown in Scheme 3, under catalyst-free, Hantzsch ester-mediated conditions, N-alkoxyphthalimides derived from a diversity of alcohols reacted well with α-trifluoromethyl styrene 2a, furnishing the targeted hydroalkylation pruducts 4a-h in 43-82% yields and 4:1->99:1 chemo-selectivity. Various α-trifluoromethyl alkenes bearing different functional groups were also readily accommodated in this transformation, and the corresponding trifluoroalkanes 4i-t were attained in good yields and chemo-selectivity. It was worth mentioning that α-trifluoromethyl styrenes with electron-deficient substituents on the aryl ring pose more challenges for delivering high chemo-selectivity, because the stabilization effect of these electron-deficient substituents would facilitate the reduction of α-CF3 benzyl radicals to carbanions, which would proceed β-fluoride elimination to afford gem-difluoroalkenes as side products. However, with our approach, a broad array of α-trifluoromethyl styrenes bearing strong electron-withdrawing groups, such as cyano, ester, ketone, and amide, were all competent substrates, thus producing trifluoromethyl alkanes 4i-o and 4s-t in excellent chemo-selectivity. This hydroalkylation reaction was found to be insensitive to steric effects, as ortho-substituted substrates also provided decent results (4l, 4r). Furthermore, late-stage modifications of naturally occurring and biologically active molecules, such as D(+)-glucose and Benzocaine was also practicable, forging products 4h, 4s and 4t in uniformly excellent chemo-selectivity. Several isotopic-labeling experiments were also conducted. When 10 equivalent of deuteroxide was added to the standard system, we did not observe any incorporation of deuterium at the α-position of the trifluoromethyl group in product 4a, implying that the α-CF3 carbanion is unlikely to be generated as an intermediate.