Intramolecular cycloadditions with high regio-and stereocontrol are important methods for the efficient assembly of complex molecular structures. Efficient routes to the synthesis of norbornadiene-tethered nitrile oxides have been developed, and their intramolecular 1, 3- dipolar cycloadditions were studied. The cycloadditions occurred in good yields for a variety of substrates and were found to be highly regio-and stereoselective.