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Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

Journal Article · · Science Advances
 [1];  [2];  [3];  [3];  [2];  [4];  [4];  [4];  [5];  [5];  [6];  [6];  [3];  [7]
  1. Wuhan Univ. (China). Institute for Advanced Studies, College of Chemistry and Molecular Sciences; DOE/OSTI
  2. Wuhan Univ. (China). Institute for Advanced Studies, College of Chemistry and Molecular Sciences; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.
  3. Chongqing Univ. (China). School of Chemistry and Chemical Engineering
  4. Wuhan Univ. (China). Institute for Advanced Studies, College of Chemistry and Molecular Sciences
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.
  6. National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
  7. Wuhan Univ. (China). Institute for Advanced Studies, College of Chemistry and Molecular Sciences; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.; Jiangxi Normal Univ., Nanchang (China). National Research Center for Carbohydrate Synthesis
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Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China (NSFC); Research Fund for the Doctoral Program of Higher Education of China; Program for Changjiang Scholars and Innovative Research Team in University; Ministry of Science and Technology of China
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1625948
Journal Information:
Science Advances, Journal Name: Science Advances Journal Issue: 9 Vol. 1; ISSN 2375-2548
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Catalytic Asymmetric Oxidative γ-Coupling of α,β-Unsaturated Aldehydes with Air as the Terminal Oxidant journal January 2018
Catalytic Asymmetric Oxidative γ-Coupling of α,β-Unsaturated Aldehydes with Air as the Terminal Oxidant journal January 2018
Copper-catalyzed aerobic benzylic sp 3 C–H oxidation mediated synthesis of 2,4,5-trisubstituted imidazoles via a domino multi-component reaction journal January 2017
Electrochemical oxidation synergizing with Brønsted-acid catalysis leads to [4 + 2] annulation for the synthesis of pyrazines journal January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Aerobic Oxidative Coupling
C-N Bond Formation
Copper-Catalyzed
DFT Calculations
EPR
XAFS