Diverse substituted pyridines and pyrimidines with high selectivity were obtained using a concise and efficient protocol developed herein. The reaction proceeds via metal-free cascade annulation of isopropene derivatives. Using isopropene derivatives as C3 synthons, NHI as the "N" source, and formaldehyde or dimethyl sulfoxide as the carbon source, this reaction realizes the efficient formation of intermolecular C-N and C-C bonds.

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