Pyrimidines 3, 7 and 13 carrying an ω-alkynyl side-chain-CR2 (CH2) nCH2C CH (R= H, CN; n= 1, 2) at the 2-position undergo intramolecular inverse electron demand Diels-Alder reactions across the C-2 and C-5 positions. Loss of hydrogen cyanide, caused by a retro- Diels-Alder reaction, from the intermediate cycloadducts leads to annelated pyridines 5, 9 and 15, respectively. Similarly, from the nitropyridines 16 the 2, 3-dihydronitro-1H-indenes ...