Transition-metal-free direct arylation: Synthesis of halogenated 2-amino-2′-hydroxy-1,1′-biaryls and mechanism by DFT calculations

Hongyin Gao, Daniel H. Ess, Muhammed Yousufuddin, László Kürti

Research output: Contribution to journalArticlepeer-review

75 Scopus citations

Abstract

A transition-metal-free, regioselective direct aryl-aryl bond-forming process for the synthesis of halogenated 2-amino-2′-hydroxy-1,1′- biaryls that are currently either inaccessible or challenging to prepare using conventional methods is disclosed. The addition of ArMgX to an o-halonitrobenzene at low temperature generates a transient N,O- biarylhydroxylamine that rapidly undergoes either [3,3]- or [5,5]-sigmatropic rearrangement in one-pot to form a 2-amino-2′-hydroxy-1,1′-biaryl or 1-amino-1′-hydroxy-4,4′-biaryl, respectively. The periselectivity is controlled by the choice of solvent and temperature. This direct arylation process is also readily scalable (1-10 mmol). DFT calculations suggest that from the N,O-biarylhydroxylamine intermediate there is a low-energy stepwise pathway that involves initial Mg-mediated N-O bond cleavage followed by pathway branching toward either [3,3]- or [5,5]-rearrangement products via C-C bond formation and rearomatization.

Original languageEnglish (US)
Pages (from-to)7086-7089
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number19
DOIs
StatePublished - May 15 2013

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Transition-metal-free direct arylation: Synthesis of halogenated 2-amino-2′-hydroxy-1,1′-biaryls and mechanism by DFT calculations'. Together they form a unique fingerprint.

Cite this