Synthesis of Josiphos-Type Bisphospholane Ligands

Tim Hammerer; Andrea Dämbkes; Wolfgang Braun; Albrecht Salzer; Giancarlo Franciò; Walter Leitner

doi:10.1055/s-0032-1316755

Synthesis, Table of Contents

Synthesis 2012; 44(17): 2793-2797
DOI: 10.1055/s-0032-1316755

paper

Synthesis of Josiphos-Type Bisphospholane Ligands

Tim Hammerer

^aInstitut für Technische Chemie und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany, Fax: +49(241)8022177 Email: francio@itmc.rwth-aachen.de Email: leitner@itmc.rwth-aachen.de

,

Andrea Dämbkes

^aInstitut für Technische Chemie und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany, Fax: +49(241)8022177 Email: francio@itmc.rwth-aachen.de Email: leitner@itmc.rwth-aachen.de

,

Wolfgang Braun

^bInstitut für Anorganische Chemie, RWTH Aachen University, Landoldtweg 1, 52074 Aachen, Germany

,

Albrecht Salzer

^bInstitut für Anorganische Chemie, RWTH Aachen University, Landoldtweg 1, 52074 Aachen, Germany

,

Giancarlo Franciò*

^aInstitut für Technische Chemie und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany, Fax: +49(241)8022177 Email: francio@itmc.rwth-aachen.de Email: leitner@itmc.rwth-aachen.de

,

Walter Leitner*

^aInstitut für Technische Chemie und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany, Fax: +49(241)8022177 Email: francio@itmc.rwth-aachen.de Email: leitner@itmc.rwth-aachen.de

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Abstract

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Abstract

Bisphospholane Josiphos-type ligands were synthesized in high yields employing electrophilic and nucleophilic phospholane synthons. Full characterization data including solid-state structures of the diastereomeric ligands are reported. These ligands resulted in active and enantioselective iridium catalysts for the asymmetric hydrogenation of imines. Pronounced cooperative effects of the chiral elements within the ligand structure were observed and enantioselectivities of up to 74% ee were achieved.

Key words

ferrocene ligands - chiral phospholane - asymmetric hydrogenation - iridium - imine hydrogenation

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References

References
1 Current address: Department of Petroleum Engineering, Texas A&M University, College Station, TX, USA.

2a Togni A, Breutel C, Schnyder A, Spindler F, Landert H, Tijani A. J. Am. Chem. Soc. 1994; 116: 4062
2b Togni A, Breutel C, Soares MC, Zanetti N, Gerfin T, Gramlich V, Spindler F, Rihs G. Inorg. Chim. Acta 1994; 222: 213

3a Hayashi T, Mise T, Fukushima M, Kagotani M, Nagashima N, Hamada Y, Matsumoto A, Kawakami S, Konishi M, Yamamoto K, Kumada M. Bull. Chem. Soc. Jpn. 1980; 53: 1138
3b Hayashi T, Yamamoto K, Kumada M. Tetrahedron Lett. 1974; 15: 4405
3c Hayashi T, Tanaka M, Ogata I. Tetrahedron Lett. 1977; 18: 295

4a Blaser H.-U, Brieden W, Pugin B, Spindler F, Studer M, Togni A. Top. Catal. 2002; 19: 3
4b Blaser HU, Federsel HJ. Asymmetric Catalysis on Industrial Scale . 2nd ed. Wiley-VCH; Weinheim: 2010

5 Marquarding D, Klusacek H, Gokel G, Hoffmann P, Ugi I. J. Am. Chem. Soc. 1970; 92: 5389

6a Blaser H.-U, Pugin B, Spindler F, Mejía E, Togni A In Privileged Chiral Ligands and Catalysts. Zhou Q.-L. Wiley-VCH; Weinheim: 2011: 93-136
6b Togni A, Halterman R. Metallocenes: Synthesis, Reactivity, Applications . Wiley-VCH; Weinheim: 1998
6c Stepnicka P. Ferrocenes: Ligands, Materials and Biomolecules . John Wiley & Sons; Chichester: 2008
6d Dai LX, Huo X.-L. Chiral Ferrocenes in Asymmetric Catalysis: Synthesis and Applications. Wiley-VCH; Weinheim: 2009
6e Gómez ArrayásR, Adrio J, Carretero JC. Angew. Chem. Int. Ed. 2006; 45: 7674
6f Colacot TJ. Chem. Rev. 2003; 103: 3101
6g Atkinson RC. J, Gibson VC, Long NJ. Chem. Soc. Rev. 2004; 33: 313

7 Braun W, Calmuschi B, Haberland J, Hummel W, Liese A, Nickel T, Stelzer O, Salzer A. Eur. J. Inorg. Chem. 2004; 2235
8 Holz J, Monsees A, Kadyrov R, Börner A. Synlett 2007; 599
9 Hammerer T, Weisgerber L, Schenk S, Stelzer O, Englert U, Leitner W, Franciò G. Tetrahedron: Asymmetry 2012; 23: 53
10 Roßenbach S. Diploma Thesis . Bergische Universität-GH Wuppertal; Germany: 1997
11 For comparing the conformational properties of Josiphos derivatives, Togni⁶ chose the torsion angles α1 and α2 defining the relative orientation with respect to the ferrocene core of the substituent at the ortho-P in the exo position and of the methyl group in the α-position, respectively.
12 Contreras RH, Peralta JE. Prog. Nucl. Magn. Reson. Spectrosc. 2000; 37: 321
13 Similar trend in ³¹P NMR was found for the two diastereomers of ferrocene-derived phosphine-phosphoramidite ligands: Hu X.-P, Zheng Z. Org. Lett. 2004; 6: 3585

14a Allen DW, Taylor BF. J. Chem. Soc., Dalton Trans. 1982; 51
14b Allen DW, Nowell IW, Taylor BF. J. Chem. Soc., Dalton Trans. 1985; 2505

15a Bilenko V, Spannenberg A, Baumann W, Komarov I, Börner A. Tetrahedron: Asymmetry 2006; 17: 2082
15b Holz J, Zayas O, Axel M, Kadyrov R, Börner A. Chem.–Eur. J. 2006; 12: 5001

16a Buergler JF, Niedermann K, Togni A. Chem.–Eur. J. 2012; 18: 632
16b Buergler JF, Togni A. Chem. Commun. 2011; 47: 1896

17 Sheldrick GM. SADABS program. University of Göttingen; Germany: 1996
18 Spek A. J. Appl. Crystallogr. 2003; 36: 7
19 Sheldrick GM. Acta Crystallogr. Sect. A 2008; 64: 112