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

Abstract

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.

The Versatile and Strategic O-Carbamate Directed Metalation Group in the Synthesis of Aromatic Molecules: An Update

“…Bavikar et al 403 reported an enantioselective total synthesis of (−)-panduratin D (500), a novel secondary metabolite against human pancreatic PANC-1 cancer cells, from commercial 3methoxyphenol (501) in nine steps with an overall yield of 5.4% (Scheme 114). Key steps include Sonogashira coupling, AoF rearrangement, and DoM to form the furanochalcone unit (506) and tandem Si−C alkyl rearrangement/Claisen−Schmidt condensation to form the chalcone structure (507). The asymmetric Diels−Alder cycloaddition of chalcone 507 and ocimene (508) promoted by a chiral boron complex provides the final chiral cyclohexene core of (−)-panduratin D (500).…”

“…The as-yet unexplored 2,7-arylation of 1,8-naphthalenediyl bis­(diethylcarbamate)­s followed by D re M or A o F of the 1,8-naphthalenediyl bis­(diethylcarbamate) compounds could provide access to a new set of interesting materials. This has been carried out for the amide analogues …”

Directed Ortho Metalation in 2021: A Tribute to Victor Snieckus (August 1, 1937–December 18, 2020)

“…His scientific contributions were immense and led to several additional industrial applications . Until recent years, he regularly published new original contributions expanding DoM chemistry . He was not only an immense scientist and teacher, always willing to discuss new aspects of chemistry, but also a very generous and eternally young and positive fellow.…”