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A dual cqd-catalysis and h-bond acceptor for controlling product selectivity and regioselectivity in symmetric/unsymmetric azoxy arenes

Hasani, M ; Sharif University of Technology | 2024

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  1. Type of Document: Article
  2. DOI: 10.1021/acs.joc.4c00373
  3. Publisher: 2024
  4. Abstract:
  5. Azoxy arenes are valuable compounds in different areas of chemistry, such as organic chemistry, medicinal chemistry, and natural product chemistry. Despite their value, the regioselective synthesis of unsymmetric azoxybenzenes has remained a real challenge in the field. Herein, the product selectivity in oxidative homocoupling of anilines into symmetric azoxybenzenes was first achieved by an asparagine-functionalized CQD catalyst. Subsequently, in the cross-coupling of anilines into the unsymmetric azoxybenzenes via an ortho H-bond acceptor (HBA) on one of the coupling anilines, the regioselectivity was effectively controlled. It was demonstrated that ortho-HBA could mechanistically establish a six-membered intramolecular hydrogen-bonded ring on an N,N′-dihydroxy intermediate. The formed hydrogen bond makes the nearby nitrogen eminently suitable for the slow dehydration step. As a result, the functional oxygen of the azoxy compound is placed far from the HBA. The o-HBA mechanism also controls the regioselectivity ratio in which 1:0 (with an intramolecular H-bonded hexagonal ring), 2:1 (with an intramolecular H-bonded pentagonal ring), and 1:1 (without an ortho-HBA) isomeric mixtures could be achieved. The HBA mechanism was exploited by different substituted anilines, and various unsymmetric azoxybenzenes were synthesized. Finally, with the aid of mechanistic studies, a plausible mechanism for the reaction was proposed. © 2024 American Chemical Society
  6. Keywords:
  7. Aniline ; Reaction intermediates ; Regioselectivity ; Aniline derivative ; Asparagine ; Azoxy derivative ; Nitrogen ; Oxygen ; Polycyclic aromatic hydrocarbon ; Azoxybenzenes ; Bond acceptors ; H-bonded ; Medicinal chemistry ; Natural products chemistry ; Organic chemistry ; Product selectivities ; Regioselective synthesis ; Symmetrics ; Catalysis ; Catalyst ; Hydrogen bond ; Reaction analysis ; Synthesis
  8. Source: Journal of Organic Chemistry ; Volume 89, Issue 19 , 2024 , Pages 13836-13846 ; 00223263 (ISSN)
  9. URL: https://pubs.acs.org/doi/10.1021/acs.joc.4c00373