Abstract Vinyl triflates 1, which are obtained easily from the corresponding ketones, react in an excess of pure nitrile (80/20 hours) to form tri-and tetra-substituted alkyl and arylpyrimidines 4 and 5 in good yields (45–87%). An isomeric mixture of pyrimidines 4 and 5 is formed from Inflate 1 when R 1≠ R 2≠ H. The reaction proceeds by nitrile-catalyzed elimination-addition mechanism.