Advertisement

Monatshefte für Chemie - Chemical Monthly

, Volume 150, Issue 2, pp 295–302 | Cite as

Copper-catalyzed conjugate addition of in situ formed alkyl boranes to α,β-unsaturated ketones

  • Bernard Mravec
  • Kristína Plevová
  • Radovan ŠebestaEmail author
Original Paper
  • 57 Downloads

Abstract

Conjugate addition of in situ formed organometallic reagents to α,β-unsaturated carbonyl compounds provides an efficient way to generate new C–C bonds. We show optimization of the copper-catalyzed conjugate addition of alkylboranes, which were formed directly in the reaction mixture by hydroboration of alkenes. We have improved the reaction conditions by employing “greener”, less hygroscopic, and higher boiling solvent, 2-methyltetrahydrofuran. We have also broadened the scope of the reaction. Furthermore, chiral ferrocenyl carbene ligands were assessed in the enantioselective version of the transformation with medium enantioselectivity 67:33 e.r.

Graphical abstract

Keywords

Cu catalysis Conjugate addition Organoborane Hydroboration 2-Methyltetrahydrofuran 

Notes

Acknowledgements

This work was supported by the Slovak Research and Development Agency under contract no. APVV-0321-12.

Supplementary material

706_2018_2309_MOESM1_ESM.docx (3.3 mb)
Supplementary material 1 (DOCX 3417 kb)

References

  1. 1.
    Alexakis A, Krause N, Woodward S (2014) Copper-catalyzed asymmetric synthesis. Wiley-VCH, WeinheimCrossRefGoogle Scholar
  2. 2.
    Krause N, Hoffmann-Röder A (2001) Synthesis:171Google Scholar
  3. 3.
    Alexakis A, Benhaim C (2002) Eur J Org Chem:3221Google Scholar
  4. 4.
    Lopez F, Minnaard AJ, Feringa BL (2007) Acc Chem Res 40:179CrossRefGoogle Scholar
  5. 5.
    Harutyunyan SR, den Hartog T, Geurts K, Minnaard AJ, Feringa BL (2008) Chem Rev 108:2824CrossRefGoogle Scholar
  6. 6.
    Alexakis A, Bäckvall JE, Krause N, Pàmies O, Diéguez M (2008) Chem Rev 108:2796CrossRefGoogle Scholar
  7. 7.
    Muller D, Alexakis A (2012) Chem Commun 48:12037CrossRefGoogle Scholar
  8. 8.
    Byrd KM (2015) Beilstein J Org Chem 11:530CrossRefGoogle Scholar
  9. 9.
    Wipf P, Smitrovich JH (1991) J Org Chem 56:6494CrossRefGoogle Scholar
  10. 10.
    Wipf P, Xu W, Smitrovich JH, Lehmann R, Venanzi LM (1991) Tetrahedron 50:1935CrossRefGoogle Scholar
  11. 11.
    Maksymowicz RM, Bissette AJ, Fletcher SP (2015) Chem Eur J 21:5668CrossRefGoogle Scholar
  12. 12.
    Takaya Y, Ogasawara M, Hayashi T (1998) Tetrahedron Lett 39:8479CrossRefGoogle Scholar
  13. 13.
    Hickmann V, Alcarazo M, Fürstner A (2010) J Am Chem Soc 132:11042CrossRefGoogle Scholar
  14. 14.
    Hirano K, Yorimitsu H, Oshima K (2007) Org Lett 9:1541CrossRefGoogle Scholar
  15. 15.
    Ohmiya H, Yoshida M, Sawamura M (2011) Org Lett 13:482CrossRefGoogle Scholar
  16. 16.
    Ohmiya H, Shido Y, Yoshida M, Sawamura M (2011) Chem Lett 40:928CrossRefGoogle Scholar
  17. 17.
    Yoshida M, Ohmiya H, Sawamura M (2012) J Am Chem Soc 134:11896CrossRefGoogle Scholar
  18. 18.
    Drusan M, Šebesta R (2014) Tetrahedron 70:759CrossRefGoogle Scholar
  19. 19.
    Toma Š, Csizmadiova J, Mečiarová M, Šebesta R (2014) Dalton Trans 43:16557CrossRefGoogle Scholar
  20. 20.
    Schaarschmidt D, Lang H (2013) Organometallics 32:5668CrossRefGoogle Scholar
  21. 21.
    Siemeling U (2012) Eur J Org Chem:3523Google Scholar
  22. 22.
    Brown HC (1961) Tetrahedron 12:117CrossRefGoogle Scholar
  23. 23.
    Brown HC, Gupta SK (1975) J Am Chem Soc 97:5249CrossRefGoogle Scholar
  24. 24.
    Brown HC, Scouten CG, Liotta R (1979) J Am Chem Soc 101:96CrossRefGoogle Scholar
  25. 25.
    Ishiyama T, Miyaura N, Suzuki A (1993) Org Synth 71:89CrossRefGoogle Scholar
  26. 26.
    Yang D, Cwynar VA, Hart DJ, Madanmohan J, Lee J, Lyons J, Caffrey M (2012) Org Synth 89:183CrossRefGoogle Scholar
  27. 27.
    Valenta P, Drucker NA, Walsh PJ (2012) Org Synth 89:527CrossRefGoogle Scholar
  28. 28.
    Monticelli S, Castoldi L, Murgia I, Senatore R, Mazzeo E, Wackerlig J, Urban E, Langer T, Pace V (2017) Monatsh Chem 148:37CrossRefGoogle Scholar
  29. 29.
    Pace V, Hoyos P, Castoldi L, Domínguez de María P, Alcántara AR (2012) ChemSusChem 5:1369CrossRefGoogle Scholar
  30. 30.
    Prat D, Wells A, Hayler J, Sneddon H, McElroy CR, Abou-Shehada S, Dunn PJ (2016) Green Chem 18:288CrossRefGoogle Scholar
  31. 31.
    Broggini D, Togni A (2002) Helv Chim Acta 85:2518CrossRefGoogle Scholar
  32. 32.
    Seo H, Park H-J, Kim BY, Lee JH, Son SU, Chung YK (2003) Organometallics 22:618CrossRefGoogle Scholar
  33. 33.
    Csizmadiová J, Mečiarová M, Almássy A, Horváth B, Šebesta R (2013) J Organomet Chem 737:47CrossRefGoogle Scholar
  34. 34.
    Sorádová Z, Máziková J, Mečiarová M, Šebesta R (2015) Tetrahedron Asymmetry 26:271CrossRefGoogle Scholar
  35. 35.
    Woltersdorf M, Kranich R, Schmalz H-G (1997) Tetrahedron 53:7219CrossRefGoogle Scholar
  36. 36.
    Wipf P, Venkatraman S (1993) J Org Chem 58:3455CrossRefGoogle Scholar
  37. 37.
    Némethová I, Sorádová Z, Šebesta R (2017) Synthesis 49:2461CrossRefGoogle Scholar
  38. 38.
    Totleben MJ, Curran DP, Wipf P (1992) J Org Chem 57:1740CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Organic Chemistry, Faculty of Natural SciencesComenius University in BratislavaBratislavaSlovakia

Personalised recommendations