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.