Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

Tetsuaki Fujihara and
Yasushi Tsuji

Review
Published 19 Sep 2018

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1. Graphical Abstract
2. Scheme 1: Optimization of the Co-catalyzed carboxylation of 1a.
  
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3. Scheme 2: Co-catalyzed carboxylation of propargyl acetates 1.
  
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4. Scheme 3: Plausible reaction mechanism for the Co-catalyzed carboxylation of propargyl acetates 1.
  
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5. Scheme 4: Optimization of the Co-catalyzed carboxylation of 3a.
  
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6. Scheme 5: Co-catalyzed carboxylation of vinyl triflates 3.
  
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7. Scheme 6: Co-catalyzed carboxylation of a sterically hindered aryl triflate 5.
  
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8. Scheme 7: Optimization of the Co-catalyzed carboxylation of 7a.
  
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9. Scheme 8: Scope of the reductive carboxylation of α,β-unsaturated nitriles 7.
  
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10. Scheme 9: Scope of the carboxylation of α,β-unsaturated carboxamides 9.
  
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11. Scheme 10: Optimization of the Co-catalyzed carboxylation of 11a.
  
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12. Scheme 11: Scope of the carboxylation of allylarenes 11.
  
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13. Scheme 12: Scope of the carboxylation of 1,4-diene derivatives 14.
  
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14. Scheme 13: Plausible reaction mechanism for the Co-catalyzed C(sp³)–H carboxylation of allylarenes.
  
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15. Scheme 14: Optimization of the Co-catalyzed carboxyzincation of 16a.
  
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16. Scheme 15: Derivatization of the carboxyzincated product.
  
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17. Scheme 16: Co-catalyzed carboxyzincation of alkynes 16.
  
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18. Scheme 17: Plausible reaction mechanism for the Co-catalyzed carboxyzincation of alkynes 16.
  
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19. Scheme 18: Co-catalyzed four-component coupling of alkynes 16, acrylates 18, CO₂, and zinc.
  
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20. Scheme 19: Proposed reaction mechanism for the Co-catalyzed four-component coupling.
  
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21. Scheme 20: Visible-light-driven hydrocarboxylation of alkynes.
  
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22. Scheme 21: Visible-light-driven synthesis of γ-hydroxybutenolides from ortho-ester-substituted aryl alkynes.
  
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23. Scheme 22: One-pot synthesis of coumarines and 2-quinolones via hydrocarboxylation/alkyne isomerization/cycliz...
  
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24. Scheme 23: Proposed reaction mechanism for the Co-catalyzed carboxylative cyclization of ortho-substituted aro...
  
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25. Scheme 24: Rh-catalyzed carboxylation of arylboronic esters 25.
  
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26. Scheme 25: Rh-catalyzed carboxylation of alkenylboronic esters 27.
  
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27. Scheme 26: Plausible reaction mechanism for the Rh-catalyzed carboxylation of arylboronic esters 25.
  
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28. Scheme 27: Ligand effect on the Rh-catalyzed carboxylation of 2-phenylpyridine 29a.
  
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29. Scheme 28: Rh-catalyzed chelation-assisted C(sp²)–H bond carboxylation with CO₂.
  
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30. Scheme 29: Reaction mechanism for the Rh-catalyzed C(sp²)–H carboxylation of 2-pyridylarenes 29.
  
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31. Scheme 30: Carboxylation of C(sp²)–H bond with CO₂.
  
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32. Scheme 31: Carboxylation of C(sp²)–H bond with CO₂.
  
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33. Scheme 32: Reaction mechanism for the Rh-catalyzed C(sp²)–H carboxylation of 2-arylphenols 34.
  
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34. Scheme 33: Hydrocarboxylation of styrene derivatives with CO₂.
  
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35. Scheme 34: Hydrocarboxylation of α,β-unsaturated esters with CO₂.
  
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36. Scheme 35: Asymmetric hydrocarboxylation of α,β-unsaturated esters with CO₂.
  
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37. Scheme 36: Proposed reaction mechanism for the Rh-catalyzed hydrocarboxylation of C–C double bonds with CO₂.
  
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38. Scheme 37: Visible-light-driven hydrocarboxylation with CO₂.
  
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39. Scheme 38: Visible-light-driven Rh-catalyzed hydrocarboxylation of C–C double bonds with CO₂.
  
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40. Scheme 39: Optimization of reaction conditions on the Rh-catalyzed [2 + 2 + 2] cycloaddition of diyne 42a and ...
  
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41. Scheme 40: [2 + 2 + 2] Cycloaddition of diyne and CO₂.
  
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42. Scheme 41: Proposed reaction pathways for the Rh-catalyzed [2 + 2 + 2] cycloaddition of diyne and CO₂.
  
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Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221

Full Text

Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin

Jun Terao,
Yohei Konoshima,
Akitoshi Matono,
Hiroshi Masai,
Tetsuaki Fujihara and
Yasushi Tsuji

Letter
Published 28 Nov 2014

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1. Graphical Abstract
2. Figure 1: Synthesis of [1]rotaxane by self-inclusion of a host–guest-linked molecule: a) short molecular leng...
  
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3. Figure 2: Synthesis of an insulated molecule via flipping phenomenon.
  
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4. Scheme 1: The synthetic route to the PMβ-CD based linked [3]rotaxane with a 5,15-di([1,1'-biphenyl]-4-yl)porp...
  
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5. Figure 3: The aromatic region of the ¹H NMR spectra of 5 at 25 °C: 1) CDCl₃, 2) CD₃OD, and 3) CD₃OD:D₂O 1:1.
  
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6. Scheme 2: Selective synthesis of fixed [3]rotaxane by Suzuki cross-coupling reaction.
  
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7. Scheme 3: The synthetic routes to precursor of PM β-CD based insulated oligothiophene.
  
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8. Scheme 4: Synthesis of dibromohexa(para-phenylene) with two PMCDs 20.
  
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9. Scheme 5: Synthesis of pseudo-linked [3]rotaxanes via double self-inclusion through flipping.
  
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10. Figure 4: The aromatic region of the ¹H NMR spectra of 5 at 25 °C: 1) CDCl₃, 2) CD₃OD, and CD₃OD/D₂O 1:1.
  
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11. Figure 5: The aromatic region of the ¹H NMR spectra of 20 at 25 °C: 1) CDCl₃, 2) CD₃OD, and CD₃OD/D₂O 1:1.
  
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12. Scheme 6: Synthesis of fixed [3]rotaxane via complexation with rhodium porphyrin.
  
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13. Figure 6: Partial ROESY NMR spectrum of 26 (400 MHz, CDCl₃) showing the NOEs between aromatic protons of the ...
  
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