Rapid synthesis of fused N-heterocycles by transition-metal-free electrophilic amination of arene C-H bonds

Hongyin Gao, Qing Long Xu, Muhammed Yousufuddin, Daniel H. Ess, Lászlõ Kürti

Research output: Contribution to journalArticle

126 Citations (Scopus)

Abstract

We disclose an efficient and operationally simple protocol for the preparation of fused N-heterocycles starting from readily available 2-nitrobiaryls and PhMgBr under mild conditions. More than two dozen N-heterocycles, including two bioactive natural products, have been synthesized using this method. A stepwise electrophilic aromatic cyclization mechanism was proposed by DFT calculations. Controlled fusion: A transition-metal-free, low-temperature, and regioselective intramolecular amination of aromatic C(sp2)-H bonds provides fused N-heterocycles. This reaction is operationally simple and scalable (1-10 mmol) and the scope of substrates is wide (see scheme). Density functional calculations indicate that a stepwise electrophilic aromatic cyclization mechanism may be operative.

Original languageEnglish (US)
Pages (from-to)2701-2705
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number10
DOIs
StatePublished - Mar 3 2014

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Amination
Cyclization
Transition metals
Biological Products
Discrete Fourier transforms
Density functional theory
Fusion reactions
Substrates
Temperature

Keywords

  • carbazoles
  • electrophilic amination
  • N-heterocycles
  • nitrobiaryls
  • regioselectivity

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Rapid synthesis of fused N-heterocycles by transition-metal-free electrophilic amination of arene C-H bonds. / Gao, Hongyin; Xu, Qing Long; Yousufuddin, Muhammed; Ess, Daniel H.; Kürti, Lászlõ.

In: Angewandte Chemie - International Edition, Vol. 53, No. 10, 03.03.2014, p. 2701-2705.

Research output: Contribution to journalArticle

Gao, Hongyin ; Xu, Qing Long ; Yousufuddin, Muhammed ; Ess, Daniel H. ; Kürti, Lászlõ. / Rapid synthesis of fused N-heterocycles by transition-metal-free electrophilic amination of arene C-H bonds. In: Angewandte Chemie - International Edition. 2014 ; Vol. 53, No. 10. pp. 2701-2705.
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