Anodic,oxidation of 2-methoxy-3,3,3-trifluoropropyl phenyl sulfide was carried out in methanol containing Et3N . 3HF to provide the corresponding alpha-methoxylated product in good yield. Nucleophilic substitution of the alpha-methoxylated product with carbon nucleophiles such as arenes and allylsilane was successfully carried out in the presence of TiCl4 and the carbon nucleophiles were introduced into the beta-position to the CF3 group in moderate yields and with high or reasonable diastereoselectivity.