Organometallic chemistry

Bernd F. Straub,
Rolf Gleiter,
Claudia Meier and
Lutz H. Gade

Editorial
Published 19 Oct 2016

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1. Figure 1: Peter Hofmann.
  
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Beilstein J. Org. Chem. 2016, 12, 2216–2221, doi:10.3762/bjoc.12.213

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Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

Anne L. Schöffler,
Ata Makarem,
Frank Rominger and
Bernd F. Straub

Full Research Paper
Published 21 Jul 2016

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1. Graphical Abstract
2. Scheme 1: Disfavored mononuclear pathway and favored dinuclear pathway in the CuAAC click reaction, according...
  
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3. Figure 1: Ball-and-stick model [42,43] of a single crystal X-ray structure of hexafluorophosphate salt 1b (CCDC 1472...
  
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4. Scheme 2: Synthesis of dinuclear copper complex 2.
  
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5. Figure 2: Time-conversion-diagram of the CuAAC reaction of benzyl azide with either phenylacetylene or ethyl ...
  
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Beilstein J. Org. Chem. 2016, 12, 1566–1572, doi:10.3762/bjoc.12.151

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Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

Regina Berg and
Bernd F. Straub

Review
Published 02 Dec 2013

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1. Graphical Abstract
2. Scheme 1: Exemplary 1,3-dipolar cycloaddition of phenylacetylene with phenyl azide [6].
  
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3. Scheme 2: CuAAC reaction of benzyl azide with (prop-2-yn-1-yloxy)benzene [12].
  
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4. Scheme 3: Bioconjugation reaction of capsid-bound azide groups with alkynyl-functionalized dye molecules (cow...
  
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5. Figure 1: Tris(triazolylmethyl)amine ligands for CuAAC applications in bioorganic chemistry: TBTA = tris[(1-b...
  
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6. Figure 2: Derivatives of 2,2’-bipyridine and 1,10-phenanthroline, commonly used ligands in CuAAC reactions un...
  
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7. Scheme 4: CuAAC reaction with copper(II) precursor salt and rate-accelerating monodentate phosphoramidite lig...
  
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8. Scheme 5: Synthesis of 1-(adamant-1-yl)-1H-1,2,3-triazol-4-ylcarbonyl-Phe-Gly-OH by solid-supported Click cat...
  
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9. Scheme 6: CuAAC reaction with re-usable copper(I)-tren catalyst [129].
  
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10. Scheme 7: CuAAC test reaction with chlorido[tris(1-benzyl-1H-1,2,3-triazol-4-yl)methanol-κ³N³]copper(I) and a...
  
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11. Scheme 8: CuAAC model reaction with [Cu₂(μ-TBTA-κ⁴N²,N³,N³’,N³’’)₂][BF₄]₂ [131].
  
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12. Scheme 9: Application of a (2-aminoarenethiolato)copper(I) complex as homogeneous catalyst for the CuAAC test...
  
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13. Scheme 10: Application of [CuBr(PPh₃)₃] as homogeneous catalyst for the CuAAC test reaction of benzyl azide wi...
  
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14. Figure 3: Phosphinite and phosphonite copper(I) complexes presented by Díez-González [144].
  
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15. Scheme 11: Effect of additives on the CuAAC test reaction with [(SIMes)CuCl] [149].
  
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16. Scheme 12: Initiation of the catalytic cycle by formation of the copper acetylide intermediate from [(ICy)₂Cu]...
  
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17. Scheme 13: Early mechanistic proposal by Sharpless [12,42].
  
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18. Scheme 14: Chemoselective synthesis of a 5-iodo-1,4-disubstituted 1,2,3-triazole [156].
  
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19. Scheme 15: Mechanistic proposals for the copper-catalyzed azide–iodoalkyne cycloaddition [156].
  
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20. Scheme 16: 1,3-Dipolar cycloaddition of 3-hexyne catalyzed by [(SIMes)CuBr] [146].
  
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21. Scheme 17: Mechanistic picture for the cycloaddition of internal alkynes catalyzed by NHC-copper(I) complexes ...
  
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22. Scheme 18: Catalytic cycle of the CuAAC reaction on the basis of the proposed mechanistic scheme by Fokin and ...
  
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23. Figure 4: Schematic representation of the single crystal X-ray structures of copper(I) acetylide complexes [Cu...
  
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24. Figure 5: Acetylide-bridged dicopper complexes with tris(heteroarylmethyl)amine ligand(s) as key intermediate...
  
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25. Scheme 19: Off-cycle equilibrium between unreactive polymeric copper(I) acetylide species (right) and reactive...
  
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26. Figure 6: Categories of tris(heteroarylmethyl)amine ligands regarding their binding ability to copper(I) ions ...
  
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27. Scheme 20: Mechanistic scheme for ligand-accelerated catalysis with tripodal tris(heteroarylmethyl)amine ligan...
  
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28. Scheme 21: Synthesis of supposed intermediates in the CuAAC’s catalytic cycle [164,187].
  
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29. Figure 7: Tetranuclear copper acetylide complexes as reported by Weiss (left) [176] and Tasker (middle) [185] and model...
  
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30. Figure 8: Gibbs free energy diagram for the computed mechanistic pathway of the CuAAC reaction starting from ...
  
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31. Figure 9: Energy diagram by Ahlquist and Fokin [125].
  
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32. Scheme 22: Mechanistic proposal for the CuAAC reaction based on DFT calculations by Fokin [125] and our group [186] ([Cu...
  
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33. Figure 10: ORTEP plot [202,203] of the X-ray powder diffraction crystal structure of (phenylethynyl)copper(I) [(PhC≡CCu)...
  
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34. Scheme 23: Synthesis of [(PhC≡CCu)₂]_n as co-product in the Glaser coupling of phenylacetylene in the presence ...
  
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35. Scheme 24: Mechanistic explanation for the isotopic enrichment in the product triazolide in the presence of th...
  
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36. Scheme 25: Homogeneous CuAAC catalysis with a bistriazolylidene dicopper complex (0.5 mol %) and comparison wi...
  
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