Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2013; 24(18): 2419-2422
DOI: 10.1055/s-0033-1339851
DOI: 10.1055/s-0033-1339851
letter
Structural Characterisation of Cu Complexes of Chiral Ferrocenyl Diphosphine Ligands
Further Information
Publication History
Received: 19 August 2013
Accepted: 22 August 2013
Publication Date:
27 September 2013 (online)
![](https://www.thieme-connect.de/media/synlett/201318/lookinside/thumbnails/10.1055-s-0033-1339851-1.jpg)
Abstract
Copper complex formation of JosiPhos-type ligands leads to extreme differences in solubility between the racemate and the enantiomers.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References
- 1a Jacobsen EN, Pfaltz A, Yamamoto H. Comprehensive Asymmetric Catalysis: Suppl. 2 . Springer-Verlag; Berlin: 2004
- 1b Walsh PJ, Kozlowski MC. Fundamentals of Asymmetric Catalysis . University Science Books; Sausalito CA (USA): 2009
- 1c Hartwig JF. Organotransition Metal Chemistry: From Bonding to Catalysis . University Science Books; Sausalito CA (USA): 2010
- 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.
- 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.
- 10a Kitajgorodskij AI. Molecular Crystals and Molecules . Academic Press; New York: 1973
- 10b For data on crystal packing see Supporting Information.
- 11a Jacques J, Collet A, Wilen SH. Enantiomers, Racemates and Resolutions . John Wiley; New York: 1981
- 11b Coquerel G. Top. Curr. Chem. 2007; 269: 1
Crystal structures of enantiopure CuBr-rev-JosiPhos (CCDC 610500) and CuBr-JosiPhos (CCDC 261573) were published in ref. 4 and in: