A general method for a new, hindered lithium diadamantylamide (LDAM) base-promoted insertion of arynes into Si-P, Si-S, Si-N, and C-C bonds is described. Arynes are generated from easily available aryl triflates and halides. Subsequent reaction of the aryne with silylated phosphines, sulfides, or amines affords the insertion products. Furthermore, a one-step synthesis of anthracenes from aryl halides and aryl ketones is also demonstrated. Cyano, aryl, alkyl, trifluoromethyl, vinyl, methoxy, chloro, fluoro, and even formyl moieties are compatible with the reaction conditions. The new lithium amide affords higher yields compared with lithium tetramethylpiperidide (LiTMP)-promoted reactions. Furthermore, the bulkiness of LDAM base essentially suppresses aryne reaction with base, allowing use of aryl halides and triflates as the limiting reagents.