We have studied the generation of cation radicals from some stannyl compounds by the oxidation with metallic oxidants and their cleavage to carbocations or carbon radicals. For example, the oxidation of α-stannyl carbamates generates their cation radicals, which are cleaved into carbocations of carbamates by the elimination of the stannyl radical. In addition, α-stannyl alkanoates are oxidized to generate the corresponding α-radicals of alkanoates and stannyl cation. Cations or radical intermediates generated in this way are utilized in the carbon-carbon bond forming reactions; they react with various olefinic compounds, such as silyl enol ethers (Eq. 1, 2). (-)-Stemonamide (1), isolated by Lin et al. from roots and rhizomes of Stemona (Stemonaceae), has been used as an anticough agent and an insecticide in traditional medicines of China and Japan. In this symposium, we report a total synthesis of (±)-stemonamide by applying the above-mentioned oxidative coupling reactions of the stannyl compounds with silyl enol ethers for the construction of the carbon framework. All the carbon units of stemonamide 1, except the methyl group, were arranged by applying our oxidative coupling of three components, 5, 6, and 11 in 4 steps (Eq. 3). The transformation of the intermediate 15 to the tricyclic compound (2) was performed under the conditions described in Eq. 4〜6. The introduction of the methyl unit proceeded stereoselectively from the convex side of 2. Thus, synthesis of (±)-stemonamide (1) was accomplished in a total of 12 steps.