Directed <i>Ortho</i> and <i>Remote</i> Metalation of Naphthalene 1,8-Diamide: Complementing S<sub><i>E</i></sub>Ar Reactivity for the Synthesis of Substituted Naphthalenes
作者:Christopher C. V. Jones、Jignesh J. Patel、Ross D. Jansen-van Vuuren、Gregory M. Ross、Bernd O. Keller、Francoise Sauriol、Gabriele Schatte、Erin R. Johnson、Victor Snieckus
DOI:10.1021/acs.orglett.1c00521
日期:2021.3.19
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
在sec -BuLi / TMEDA条件下生成1,8-萘二酰胺2的单阴离子和二阴离子物种,并用多种亲电试剂捕集,得到2-和2,7-取代的产物3和4。使用Suzuki-Miyaura交叉偶联,将单碘和二碘化产物分别转化为相应的2-芳基(5)和2,7-二芳基(6)产物。通过VT NMR建立2的酰胺-酰胺旋转势垒,并确保了通过远程金属化获得的芴酮结构9的结构。