Directed Ortho and Remote Metalation of Naphthalene 1,8-Diamide: Complementing S E Ar Reactivity for the Synthesis of Substituted Naphthalenes.

Mono- and dianion species of 1,8-naphthalene diamide 2 were generated under sec -BuLi/TMEDA conditions and trapped with a variety of electrophiles to give 2- and 2,7- substituted products 3 and 4 . Using Suzuki-Miyaura cross-coupling, mono- and di-iodinated products were converted into the corresponding 2-aryl ( 5 ) and 2,7-diaryl ( 6 ) products, respectively. The amide-amide rotation barrier of 2 was established by VT NMR, and the structure of fluorenone structure 9 , obtained by remote metalation, was secured.