A silver‐catalyzed three‐component coupling reaction of amines, 2‐isocyanobenzaldehydes, and 2,2,2‐trifluorodiazoethane has been developed. This reaction provides an efficient method for the construction of CF3‐containing dihydroquinazolines. On the basis of this reaction, using trifluorodiazoethyl‐substituted dihydroquinazolines as synthons, trifluoromethyl‐substituted indolo[1,2‐c]quinazolines were prepared in high yields via a TBHP/KI‐mediated sequential intramolecular cyclization and aromatization process.

A novel copper-catalyzed cascade cyclization reaction of 3-aminocyclobutenones with electron-deficient internal alkynes has been developed. This reaction provides a new method for the synthesis of fully substituted indoles by formation of four new bonds and two rings in a single step.