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

Romain Costil, Harvey J.A. Dale, Natalie Fey, George Whitcombe, Johnathan V. Matlock*, Jonathan Clayden

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

22 Citations (Scopus)
290 Downloads (Pure)

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.

Original languageEnglish
Pages (from-to)12533-12537
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number41
Early online date6 Sep 2017
DOIs
Publication statusE-pub ahead of print - 6 Sep 2017

Keywords

  • atropisomerism
  • diarylamines
  • Smiles rearrangement

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