Heavily Substituted Atropisomeric Diarylamines by Unactivated Smiles Rearrangement of N‐Aryl Anthranilamides

Abstract

Diarylamines find use as metal ligands and as structural components of drug molecules, and are commonly made by metal catalyzed C-N coupling. However, the limited tolerance to steric hindrance of these couplings restricts the synthetic availability of more substituted diarylamines. Here we report a remarkable variant of the Smiles rearrangement that employs readily accessible N-aryl anthranilamides as precursors to diarylamines. Conformational predisposition of the anthranilamide starting material brings the aryl rings into proximity and allows the rearrangement to take place despite the absence of electron-withdrawing substituents, and even with sterically encumbered doubly ortho-substituted substrates. Some of the diarylamine products are resolvable into atropisomeric enantiomers, and are the first simple diarylamines to display atropisomerism.

Interplay of Supramolecular Chemistry and Photochemistry with Palladium-Catalyzed Ethylene Polymerization

“…The corresponding methylated ligands (L1 Me -L4 Me ) were synthesized in high yields through reactions between NaH and CH 3 I. 37 Pd complexes (Pd1-Pd4 and Pd1 Me -Pd4 Me ) were obtained in 61-89% yields from the reaction of these ligands with one equivalent of (COD)PdMeCl (COD = 1,5-cyclooctadiene). The ligands (L1-L4 and L1 Me -L4 Me ) were characterized by 1 H NMR, 13 C NMR, and electrospray ionization mass spectrometry…”

Concerted Nucleophilic Aromatic Substitution Reactions

“…Prior to this most recent work, Clayden et al. had studied extensive alternative applications of these aryl transfer reactions, notably in ring‐expansion reactions, for example, with substrates 240 , 241 . Although Hammett plots are not reported for these series, the analogy to the amino acid cases just discussed make it highly likely that they follow cS N Ar pathways through transition states 244 .…”

Konzertierte nukleophile aromatische Substitutionen

“…Dieser jüngsten Arbeit vorangehend haben Clayden et al. umfangreiche alternative Anwendungen dieser Aryltransferreaktionen untersucht, insbesondere bei Ringexpansionsreaktionen, z. B. mit den Substraten 240 und 241 .…”