A novel synthesis method was developed for developing functionalized indolizines. In this reaction, 2-(pyridin-2-yl)acetate derivatives and N,N-dimethylenamine ketones were used as substrates. All these processes were enabled by heating a mixture of starting materials in toluene and in the presence of I2 under air. Cascade reaction resulted in the formation of two bonds and cleavage of one bond in one pot. Consequently, a number of functionalized indolizines were produced via a cascade reaction. This protocol can be used to synthesize functionalized unsymmetrical 2,4-diarylpyridines. Moreover, it is suitable for combinatorial and parallel syntheses of indolizines derivatives in a one-pot reaction and it is not a tedious multi-step reaction.