Application of Sequential Ring‐Opening, and Ring‐Closing Metathesis or Ring‐Rearrangement Metathesis to Design Oxacycles and Azacycles

Abstract We report a concise and simple synthetic approach to oxacycles, azacycles and aza‐propellanes starting with endo / exo ‐nadic anhydride via olefin metathesis as a key step. This methodology relies on the usage of Lewis acid mediated allylation of the hydroxy derivatives followed by ring‐opening metathesis (ROM) and ring‐closing metathesis (RCM) to assemble fused oxacycles and azacycles. Moreover, this methodology generates diverse skeletons such as propellanes, highly fused azacycles. Interestingly, some of these heterocyclic frames constitute the basic core of biologically active natural products.