Synlett 2013; 24(18): 2419-2422
DOI: 10.1055/s-0033-1339851
letter
© Georg Thieme Verlag Stuttgart · New York

Structural Characterisation of Cu Complexes of Chiral Ferrocenyl Diphos­phine Ligands

Francesca Caprioli
a  Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands   Fax: +31(50)3634296   Email: s.harutyunyan@rug.nl   Email: a.j.minnaard@rug.nl
,
Martin Lutz
b  Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
,
Auke Meetsma
a  Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands   Fax: +31(50)3634296   Email: s.harutyunyan@rug.nl   Email: a.j.minnaard@rug.nl
,
Adriaan J. Minnaard
a  Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands   Fax: +31(50)3634296   Email: s.harutyunyan@rug.nl   Email: a.j.minnaard@rug.nl
,
Syuzanna R. Harutyunyan*
a  Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands   Fax: +31(50)3634296   Email: s.harutyunyan@rug.nl   Email: a.j.minnaard@rug.nl
› Author Affiliations
Further Information

Publication History

Received: 19 August 2013

Accepted: 22 August 2013

Publication Date:
27 September 2013 (online)


Abstract

Copper complex formation of JosiPhos-type ligands leads to extreme differences in solubility between the racemate and the enantiomers.

Supporting Information

 
  • References

    • 2a Blaser H.-U, Pugin B, Splinder F, Thommen M. Acc. Chem. Res. 2007; 40: 1240
    • 2b Knowles WS, Sabacky MJ, Vineyard BD, Weinkauff DJ. J. Am. Chem. Soc. 1975; 97: 2567
    • 2c Kagan HB, Dang T.-P. J. Am. Chem. Soc. 1972; 94: 6429
    • 2d Miyashita A, Yasuda A, Takaya H, Toriumi K, Ito T, Souchi T, Noyori R. J. Am. Chem. Soc. 1980; 102: 7932
    • 2e Noyori R. Angew. Chem. Int. Ed. 2002; 41: 2008
    • 2f Burk MJ. J. Am. Chem. Soc. 1991; 113: 8518
    • 2g Burk MJ. Acc. Chem. Res. 2000; 33: 363
    • 2h Blaser HU, Malan C, Pugin B, Spindler F, Steiner H, Studer M. Adv. Synth. Catal. 2003; 345: 103
    • 2i Crepy KV. L, Imamoto T. Adv. Synth. Catal. 2003; 345: 79
    • 2j Genet JP. Acc. Chem. Res. 2003; 36: 908
    • 2k Tang WJ, Zhang XM. Chem. Rev. 2003; 103: 3029
    • 2l Yoon TP, Jacobsen EN. Science 2003; 299: 1691
    • 2m Pfaltz A, Drury WJ. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 5723
    • 2n Ireland T, Grossheimann G, Wieser-Jeunesse C, Knochel P. Angew. Chem. Int. Ed. 1999; 38: 3212
    • 2o Ireland T, Tappe K, Grossheimann G, Knochel P. Chem. Eur. J. 2002; 8: 843
    • 3a Madduri AV. R, Harutyunyan SR, Minnaard AJ. Angew. Chem. Int. Ed. 2012; 51: 3164
    • 3b Madduri AV. R, Minnaard AJ, Harutyunyan SR. Chem. Commun. 2012; 48: 1478
    • 3c Madduri AV. R, Minnaard AJ, Harutyunyan SR. Org. Biomol. Chem. 2012; 10: 2878
    • 3d Caprioli F, Madduri AV. R, Minnaard AJ, Harutyunyan SR. Chem. Commun. 2013; 49: 5450
  • 4 Initial spectroscopic studies of enantiopure ferrocenyl ligands were reported in our earlier work: Harutyunyan SR, López F, Browne WR, Correa A, Peña D, Badorrey R, Meetsma A, Minnaard AJ, Feringa BL. J. Am. Chem. Soc. 2006; 128: 9103
  • 5 For details see Supporting Information.

    • Crystal structures of enantiopure CuBr-rev-JosiPhos (CCDC 610500) and CuBr-JosiPhos (CCDC 261573) were published in ref. 4 and in:
    • 6a López F, Harutyunyan SR, Meetsma A, Minnaard AJ, Feringa BL. Angew. Chem. Int. Ed. 2005; 44: 2752
    • 6b An improved quality crystal structure was obtained for CuBr-rev-JosiPhos (CCDC 909405) during this study.
  • 7 CCDC 908802, CCDC 908803, CCDC 908804 and CCDC 909403 contain the supplementary crystallographic data of the corresponding complexes: rac-CuBr-rev-JosiPhos, rac-CuBr-JosiPhos, rac-CuBr-TaniaPhos and enantiopure CuBr-TaniaPhos, presented in this paper. For the crystal structure of enantiopure CuBr-TaniaPhos (CCDC 909403), see Supporting Information.
  • 8 Due to the extremely low solubility of the racemic Cu complex of rev-JosiPhos, crystals were obtained by doping one enantiomer in CH2Cl2 solution into poly(ethylene oxide) hydrogel followed by addition, as an antisolvent, of a solution of the opposite enantiomer in toluene. See: Choquesillo-Lazarte D, García-Ruiz JM. J. Appl. Cryst. 2011; 44: 172
  • 9 The structure of rac-CuBr-rev-JosiPhos is located on an inversion centre: the centrosymmetric dimer is the ‘meso’ form.
    • 12a Satyanarayana T, Ferber B, Kagan HB. Org. Lett. 2007; 9: 251
    • 12b Liu S, Wolf C. Org. Lett. 2007; 9: 2965
    • 12c Li N, Chen X.-H, Zhou S.-M, Luo S.-W, Song J, Ren L, Gong L.-Z. Angew. Chem. Int. Ed. 2010; 49: 6378