Directed <i>ortho</i> Metalation Strategies. Effective Regioselective Routes to 1,2‑, 2,3‑, and 1,2,3-Substituted Naphthalenes

The regioselective synthesis of 2,3-di- and 1,2,3-trisubstituted naphthalenes via Directed <i>ortho</i> Metalation (D<i>o</i>M) strategies of <i>N</i>,<i>N</i>-diethyl-<i>O</i>-naphthyl-2-carbamate (<b>1</b>) is presented. Sequential LiTMP metalation–electrophile quench and <i>s</i>-BuLi/TMEDA (or <i>t</i>-BuLi)-electrophile quench of naphthyl-2-carbamate <b>1</b> provides a general route to contiguously substituted naphthalenes (<b>6</b>) with full regioselectivity. Further derivatization via <i>ipso</i>-halodesilylation and Suzuki–Miyaura cross-coupling leads ultimately to substituted halonaphthalenes and benzonaphthopyranones (<b>9</b>)