Monatshefte für Chemie - Chemical Monthly

, Volume 144, Issue 4, pp 523–529 | Cite as

Expanding the oxidative chemistry of organocopper reagents: facile oxidative cross-coupling of copper acetylides with arylboronic acids

  • Florian Verna
  • Céline Guissart
  • Jonathan Pous
  • Gwilherm Evano
Original Paper


We have developed an efficient procedure for oxidative cross-coupling between arylboronic acids and alkynylcopper reagents. Upon simple addition of 1,10-phenanthroline in the presence of oxygen, these highly stable, readily available polymeric reagents are easily activated and transfer their alkynyl group after subsequent transmetallation with the boronic acid. These results further expand the oxidative chemistry of organocopper compounds together with providing a user-friendly entry to diaryl acetylenes.

Graphical abstract


Organocopper reagents Copper acetylides Oxidative coupling Boronic acids Alkynes Transmetallation 



We are grateful to the Université Libre de Bruxelles (ULB) for financial support. GE is indebted to Prof. Ivan Jabin for his most generous help during his installation at the ULB.


  1. 1.
    Glaser C (1870) Justus Liebigs Ann Chem 154:137CrossRefGoogle Scholar
  2. 2.
    Hay AS (1960) J Org Chem 25:1275CrossRefGoogle Scholar
  3. 3.
    Hay AS (1962) J Org Chem 27:3320CrossRefGoogle Scholar
  4. 4.
    Whitesides GM, San Filippo J, Casey CP, Panek EJ (1967) J Am Chem Soc 89:5302Google Scholar
  5. 5.
    Whitesides GM, Fischer WF, San Filippo J, Bashe RW, House HO (1969) J Am Chem Soc 91:4871Google Scholar
  6. 6.
    Mandeville WH, Whitesides GM (1974) J Org Chem 39:400CrossRefGoogle Scholar
  7. 7.
    Surry DS, Spring DA (2006) Chem Soc Rev 35:218CrossRefGoogle Scholar
  8. 8.
    Aves SJ, Spring DR (2009) Oxidation of organocopper compounds. In: Rappoport Z, Marek I (eds), Patai Series: the chemistry of functional groups. The chemistry of organocopper compounds, vol 24. Wiley, Chichester, p 585Google Scholar
  9. 9.
    Lipshutz BH, Siegmann K, Garcia E, Kayser F (1993) J Am Chem Soc 115:9276CrossRefGoogle Scholar
  10. 10.
    Dubbaka SR, Kienle M, Mayr H, Knochel P (2007) Angew Chem Int Ed 46:9093CrossRefGoogle Scholar
  11. 11.
    Surry DS, Su X, Fox DJ, Franckevicius V, Macdonald SJF, Spring DJ (2005) Angew Chem Int Ed 44:1870CrossRefGoogle Scholar
  12. 12.
    Surry DS, Fox DJ, Macdonald SJF, Spring DJ (2005) Chem Commun p 2589Google Scholar
  13. 13.
    Aves SJ, Pike KG, Spring DR (2010) Synlett p 2839Google Scholar
  14. 14.
    Yamamoto H, Maruoka K (1980) J Org Chem 45:2739CrossRefGoogle Scholar
  15. 15.
    Iwao M, Reed JN, Snieckus V (1982) J Am Chem Soc 104:5531CrossRefGoogle Scholar
  16. 16.
    Alberti A, Canè F, Dembech P, Lazzari D, Ricci A, Seconi G (1996) J Org Chem 61:1677CrossRefGoogle Scholar
  17. 17.
    Canè F, Brancaleoni D, Dembech P, Ricci A, Seconi G (1997) Synthesis p 545Google Scholar
  18. 18.
    del Amo V, Dubbaka SR, Krasovskiy A, Knochel P (2006) Angew Chem Int Ed 45:7838CrossRefGoogle Scholar
  19. 19.
    Boudet N, Dubbaka SR, Knochel P (2008) Org Lett 10:1715CrossRefGoogle Scholar
  20. 20.
    Kienle M, Dubbaka SR, del Amo V, Knochel P (2007) Synthesis p 1272Google Scholar
  21. 21.
    Kienle M, Dunst C, Knochel P (2009) Org Lett 11:5158CrossRefGoogle Scholar
  22. 22.
    Litvinas ND, Fier PS, Hartwig JF (2012) Angew Chem Int Ed 51:536CrossRefGoogle Scholar
  23. 23.
    Novák P, Lishchynskyi A, Grushin VV (2012) Angew Chem Int Ed 51:7767CrossRefGoogle Scholar
  24. 24.
    Zanardi A, Nokinov MA, Martin E, Benet-Buchholz J, Grushin VV (2012) J Am Chem Soc 133:20901CrossRefGoogle Scholar
  25. 25.
    Coste A, Karthikeyan G, Couty F, Evano G (2009) Angew Chem Int Ed 48:4381CrossRefGoogle Scholar
  26. 26.
    Jouvin K, Couty F, Evano G (2010) Org Lett 12:3272CrossRefGoogle Scholar
  27. 27.
    Jouvin K, Evano G (2011) Chim Oggi 29:31Google Scholar
  28. 28.
    Laouiti A, Rammah MM, Rammah MB, Marrot J, Couty F, Evano G (2012) Org Lett 14:6CrossRefGoogle Scholar
  29. 29.
    Jouvin K, Bayle A, Legrand F, Evano G (2012) Org Lett 14:1652CrossRefGoogle Scholar
  30. 30.
    Jouvin K, Coste A, Bayle A, Legrand F, Karthikeyan G, Tadiparthi K, Evano G (2012) Organometallics 31:7933CrossRefGoogle Scholar
  31. 31.
    Jouvin K, Heimburger J, Evano G (2012) Chem Sci 3:756CrossRefGoogle Scholar
  32. 32.
    Laouiti A, Jouvin K, Rammah MM, Rammah MB, Evano G (2012) Synthesis 44:1491CrossRefGoogle Scholar
  33. 33.
    Royer EC, Barral MC, Moreno V, Santos A (1981) J Inorg Nucl Chem 43:705CrossRefGoogle Scholar
  34. 34.
    Pan C, Luo F, Wang W, Ye Z, Cheng J (2009) Tetrahedron Lett 50:5044CrossRefGoogle Scholar
  35. 35.
    Rao H, Fu H, Jiang Y, Zhao Y (2010) Adv Synth Catal 352:458CrossRefGoogle Scholar
  36. 36.
    Yasukawa T, Miyamura H, Kobayashi S (2011) Org Biomol Chem 9:6208CrossRefGoogle Scholar
  37. 37.
    Zou G, Zhu J, Tang J (2003) Tetrahedron Lett 44:8709CrossRefGoogle Scholar
  38. 38.
    Yang F, Wu Y (2007) Eur J Org Chem p 3476Google Scholar
  39. 39.
    Zhou MB, Wei WT, Xie YX, Lei Y, Li JH (2010) J Org Chem 75:5653Google Scholar
  40. 40.
    Nie X, Liu S, Zong Y, Sun P, Bao J (2011) J Organomet Chem 696:1570CrossRefGoogle Scholar
  41. 41.
    Qian D, Zhang J (2011) Beilstein J Org Chem 7:808CrossRefGoogle Scholar
  42. 42.
    You XL, Hu T, Xu L (2012) Lett Org Chem 9:300CrossRefGoogle Scholar
  43. 43.
    Mitsudo K, Shiraga T, Mizukawa JI, Suga S, Tanaka H (2010) Chem Commun 46:9256CrossRefGoogle Scholar
  44. 44.
    Rao MLN, Jadhav DN, Dasgupta P (2010) Org Lett 12:2048CrossRefGoogle Scholar
  45. 45.
    Yang D, Li B, Yang H, Fu H, Hu L (2011) Synlett p 702Google Scholar
  46. 46.
    Fabrizi G, Goggiamani A, Sferrazza A, Cacchi S (2010) Angew Chem Int Ed 49:4067CrossRefGoogle Scholar
  47. 47.
    Huang H, Liu H, Jiang H, Chen K (2008) J Org Chem 73:6037CrossRefGoogle Scholar
  48. 48.
    Sato M, Mogi E, Katada M (1995) Organometallics 14:4837CrossRefGoogle Scholar
  49. 49.
    Tang BX, Wang F, Li JH, Xie YX, Zhang MB (2007) J Org Chem 72:6294CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Wien 2013

Authors and Affiliations

  • Florian Verna
    • 1
  • Céline Guissart
    • 1
  • Jonathan Pous
    • 1
  • Gwilherm Evano
    • 1
  1. 1.Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie OrganiquesUniversité Libre de BruxellesBrusselsBelgium

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