In the course of our investigations on the synthesis of heterocyclic compounds using organosilicon reagents,2,3 we reported that an N-silyl-1-aza-allyl anion generated from an a-functionalized silane directly gave an Rf substituted pyridine derivative,4 and that the a-functionalized silane and the N-silyl-1-aza-allyl anion were useful building blocks for the construction of heterocyclic compounds. In the previous work, we reported a convenient novel method to prepare 2-pentafluoroethyl-3-trifluoromethyl-4H-quinolizin-4-one derivatives and 1H-pyrido[2,1-b]benzothiazol(or benzoxazol)-1-one derivatives in high yields by a one-pot reaction of 2-(trimethylsilylmethyl)pyridines (or the corresponding benzothiazole and benzoxazole derivatives) with perfluoro(2-methyl-2-pentene) in the presence of potassium fluoride in tetrahydrofuran, as shown in Scheme 1.1 Quinolizine or quinolizinium ring systems frequently exist in alkaloids, in most cases in the reduced form.5 They have attracted the attention of many researchers because of their useful medicinal activity, such as anthelmintic,6 anti-inflammatory,7 antispasmodic8 and antiulcerogenic activity.9 Therefore, it is of importance to develop a method for constructing a Rf substituted quinolizinium ring system, which is expected having stronger physiological activity than that of the parent compound. As an extension of this research, we wish to report in this paper a reaction of methyl perfluoro(2-methylprop-1-enyl) ether 1 with 2-(trimethylsilylmethyl)pyridines 3 in comparison with a reaction of perfluoro(2-methylpent-2-ene) 2.