Although the full conversion of hydrosilylation of 1a in toluene required 110 °C, the yield of 3a decreased (entry 2). 1,2-Dichloroethane (1,2-DCE) was selected as the solvent, and 3a was obtained in 76% yield (entry 3). The use of Togni reagent II (2b) instead of 2a resulted in the formation of 3a in 46% yield (entry 4). However, Umemoto reagents I (2c) and II (2d) were unsuitable (entries 5 and 6). We considered that the low solubility of Umemoto reagents 2c and 2d in 1,2-DCE resulted in the use of dimethyl sulfoxide as a co-solvent (entry 7). Although the efficiency of the reaction was improved, the yield was lower than those of Togni reagents 2a and 2b. The addition of 2a without cooling resulted in a slight decrease in the yield, while a lower temperature did not improve the yield of 3a (entries 8 and 9). Under the optimized conditions, various substrates were subjected to trifluoromethylation (Scheme 2). 3-Trifluoromethyl quinoline (3a) was obtained in 76% yield. The reactions of substrates 1b-1d bearing aryl ether, silyl ether, or pivalate produced the corresponding products 3b-3d in good yields. Arylsilane 1e was tolerated, giving the 3-trifluoromethylated product 3e in 66% yield. This reaction was applicable to a variety of substrates with functional groups. Carbon-halogen bonds were tolerated under the reaction conditions, yielding a moderate to good amount of the desired products 3f-3k without loss of halogen atoms. Despite steric hindrance, 2-phenyl quinoline (1l) was also successfully converted to the desired product 3l in 49% yield. 4-Position-substituted substrates were converted to the corresponding 3-trifluoromethylated products to avoid steric hindrance. 4-Phenylquinoline (1m) was reacted with hydrosilane at 50 °C for 7 h, and the resulting mixture was treated with 2a to obtain the desired product 3m in 38% yield. The reaction of 4-phenoxyquinoline (1n) proceeded under standard reaction conditions, and the 3-trifluoromethylated product 3n was obtained in 61% yield. 3-Trifluoromethyl benzo [f]quinoline 3o was obtained in moderate yield. In the case of isoquinoline (1p), hydrosilylation was carried out at 110 °C for 16 h in chloroform, and the resulting mixture was reacted with 2a to obtain the corresponding product 3p in 34% yield. In these cases, the formation of 1,2-dihydroquinoline was confirmed by 1 H NMR measurements of the reaction mixture (for details, see Supporting Information). The reaction of 3-phenylpyridine (1q) afforded the corresponding product 3q in moderate yields. 8-Methylquinoline did not produce the desired 3-trifluoromethylated product because hydrosilylation did not proceed, probably because of steric hindrance. This method can be applied for the introduction of perfluoroalkyl groups at the 3-position of the pyridine ring (Scheme 3). 6-Bromo-3-pentafluoroethylquinoline ( ) and 6-bromo-3-heptafluoropropylquinoline (5) were obtained in 72% and 69% yields, respectively.