Synthesis 2012; 44(22): 3534-3542
DOI: 10.1055/s-0032-1316796
paper
© Georg Thieme Verlag Stuttgart · New York

Ligand Control of the Cobalt-Catalysed 1,4-Hydrovinylation Reaction

Marion Arndt
a  Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany   Email: Hilt@chemie.uni-marburg.de   Fax: +49(6421)2825677
,
Mehmet Dindaroğlu
b  Department für Chemie, Universität zu Köln, Greinstr. 4, 50939 Cologne, Germany
,
Hans-Günther Schmalz
b  Department für Chemie, Universität zu Köln, Greinstr. 4, 50939 Cologne, Germany
,
Gerhard Hilt*
a  Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany   Email: Hilt@chemie.uni-marburg.de   Fax: +49(6421)2825677
› Author Affiliations
Further Information

Publication History

Received: 17 September 2012

Accepted: 18 September 2012

Publication Date:
02 October 2012 (online)


Abstract

The application of cobalt catalysts to the hydrovinylation of unsymmetrical alkenes and 1,3-dienes was investigated using modular phosphine-phosphite ligands to evaluate the influence of the ligands on the regioselectivity of the reaction. While a ligand with a TADDOL subunit (SchmalzPhos) gave the best results for the β-4 regioisomer, the corresponding BINOL-derived ligand gave predominantly the β-1 regioisomer. The application of (E)-2-methylpenta-1,3-diene in combination with the (nonracemic) BINOL-derived ligand generated the β-4 regioisomer in excellent yields and very high regioselectivities for a number of terminal alkenes bearing various functional groups. In one case, the enantiomeric excess of a chiral product, i.e. a 3,5-dimethylhexa-1,4-diene derivative, was determined by chiral RP-HPLC to be 78% ee.

 
  • References


    • For reviews, see:
    • 1a Hess W, Treutwein J, Hilt G. Synthesis 2008; 3537
    • 1b Omae I. Appl. Organomet. Chem. 2007; 21: 318
    • 1c Jeganmohan M, Cheng C.-H. Chem.–Eur. J. 2008; 14: 10876
    • 1d Laschat S, Becheanu A, Bell T, Baro A. Synlett 2005; 2547

    • For 1,2-hydrovinylations catalysed by Ni, see:
    • 1e Ho C.-Y, He L. Angew. Chem. Int. Ed. 2010; 49: 9182
    • 1f Zhang Q, Zhu S.-F, Cai Y, Wang L.-X, Zhou Q.-L. Sci. China Chem. 2010; 53: 1899
    • 1g Lassauque N, Franciò G, Leitner W. Adv. Synth. Catal. 2009; 351: 3133
    • 1h Barta K, Eggenstein M, Hölscher M, Franciò G, Leitner W. Eur. J. Org. Chem. 2009; 6198
    • 1i Barta K, Hölscher M, Franciò G, Leitner W. Eur. J. Org. Chem. 2009; 4102
    • 1j Smith CR, Lim HJ, Zhang A, RajanBabu TV. Synthesis 2009; 2089
    • 1k Lassauque N, Franciò G, Leitner W. Eur. J. Org. Chem. 2009; 3199
    • 1l Joseph J, RajanBabu TV, Jemmis ED. Organometallics 2009; 28: 3552
    • 1m Smith CR, RajanBabu TV. J. Org. Chem. 2009; 74: 3066
    • 1n Saha B, Smith CR, RajanBabu TV. J. Am. Chem. Soc. 2008; 130: 9000
    • 1o Zhang Q, Zhu S.-F, Qiao X.-C, Wang L.-X, Zhou Q.-L. Adv. Synth. Catal. 2008; 350: 1507

    • For 1,2-hydrovinylations catalysed by Pd, see:
    • 1p Ayora I, Ceder RM, Espinel M, Muller G, Rocamora M, Serrano M. Organometallics 2011; 30: 115
    • 1q Rodríguez L.-I, Rossell O, Seco M, Orejón A, Masdeu-Bultó AM. J. Organomet. Chem. 2008; 693: 1857

    • For 1,2-hydrovinylations catalysed by Co, see:
    • 1r Grutters MM. P, van der Vlugt JI, Pei Y, Mills AM, Lutz M, Spek AL, Müller C, Moberg C, Vogt D. Adv. Synth. Catal. 2009; 351: 2199
    • 1s Grutters MM. P, Müller C, Vogt D. J. Am. Chem. Soc. 2006; 128: 7414

    • For 1,2-hydrovinylations catalysed by Pt, see:
    • 1t Serra D, Cao P, Cabrera J, Padilla R, Rominger F, Limbach M. Organometallics 2011; 30: 1885
    • 1u Cucciolito ME, D’Amora A, Vitagliano A. Organometallics 2005; 24: 3359

    • For 1,2-hydrovinylations catalysed by Ir, see:
    • 1v Oxgaard J, Bhalla G, Periana RA, Goddard III WA. Organometallics 2006; 25: 1618
    • 1w Bhalla G, Oxgaard J, Goddard III WA, Periana RA. Organometallics 2005; 24: 5499

    • For 1,2-hydrovinylations catalysed by Ru, see:
    • 1x Jiang G, List B. Chem. Commun. 2011; 47: 10022
    • 1y Gavenonis J, Arroyo RV, Snapper ML. Chem. Commun. 2010; 46: 5692
    • 1z Sanchez Jr RP, Connell BT. Organometallics 2008; 27: 2902
    • 1aa Kondo T, Takagi D, Tsujita H, Ura Y, Wada K, Mitsudo T.-a. Angew. Chem. Int. Ed. 2007; 46: 5958

    • For Fe-catalysed hydrovinylations, see:
    • 1ab Russell SK, Lobkovsky E, Chirik PJ. J. Am. Chem. Soc. 2011; 133: 8858
    • 1ac Small BL, Marcucci AJ. Organometallics 2001; 20: 5738

      For recent general reviews on Co-catalysed reactions, see:
    • 2a Hilt G. Eur. J. Org. Chem. 2012; 4441
    • 2b RajanBabu TV. Chem. Rev. 2003; 103: 2845
    • 2c RajanBabu TV. Synlett 2009; 853

    • For Co-catalysed 1,4-hydrovinylations, see:
    • 2d Kersten L, Hilt G. Adv. Synth. Catal. 2012; 354: 863
    • 2e Erver F, Hilt G. Org. Lett. 2011; 13: 5700
    • 2f Arndt M, Reinhold A, Hilt G. J. Org. Chem. 2010; 75: 5203
    • 2g Kersten L, Roesner S, Hilt G. Org. Lett. 2010; 12: 4920
    • 2h Hilt G, Arndt M, Weske DF. Synthesis 2010; 1321
    • 2i Hilt G, Treutwein J. Chem. Commun. 2009; 1395
    • 2j Hilt G, Danz M, Treutwein J. Org. Lett. 2009; 11: 3322
    • 2k Hilt G, Lüers S, Schmidt F. Synthesis 2004; 634
  • 3 Hilt G, Roesner S. Synthesis 2011; 662

    • SchmalzPhos = (3aR,8aR)-6-[3-(diphenylphosphino)bi-phenyl-2-yloxy]-2,2-dimethyl-4,4,8,8-tetraphenyltetra-hydro[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepine. For synthetic applications, see also:
    • 4a Kranich R, Eis K, Geis O, Mühle S, Bats JW, Schmalz H.-G. Chem.–Eur. J. 2000; 6: 2874
    • 4b Blume F, Zemolka S, Fey T, Kranich R, Schmalz H.-G. Adv. Synth. Catal. 2002; 344: 868
    • 4c Robert T, Velder J, Schmalz H.-G. Angew. Chem. Int. Ed. 2008; 47: 7718
    • 4d Lölsberg W, Ye S, Schmalz H.-G. Adv. Synth. Catal. 2010; 352: 2023
    • 4e Robert T, Abiri Z, Wassenaar J, Sande AJ, Romanski S, Neudörfl J.-M, Schmalz H.-G, Reek JN. H. Organometallics 2010; 29: 478
    • 4f Robert T, Abiri Z, Sandee AJ, Schmalz H.-G, Reek JN. H. Tetrahedron: Asymmetry 2010; 21: 2671
    • 4g Bohn MA, Schmidt A, Hilt G, Dindaroğlu M, Schmalz H.-G. Angew. Chem. Int. Ed. 2011; 50: 9689
  • 5 Arndt M, Dindaroğlu M, Schmalz H.-G, Hilt G. Org. Lett. 2011; 13: 6236
  • 6 For the synthesis of the ligands L1 and L3, see: Velder J, Robert T, Weidner I, Neudörfl J.-M, Lex J, Schmalz H.-G. Adv. Synth. Catal. 2008; 350: 1309
  • 7 Moreau B, Wu JY, Ritter T. Org. Lett. 2009; 11: 337
    • 8a Starting material 14 was obtained from 2-methylpentane-2,4-diol as a mixture with 4-methylpenta-1,3-diene, following the procedure reported by: Williams PH, Finch de HV, Ballard SA. (Shell Development Company) GB 572602 1945
    • 8b The side product 4-methylpenta-1,3-diene is unreactive under the reaction conditions and remains unchanged.
  • 9 Hilt G, Hess W, Harms K. Org. Lett. 2006; 8: 3287
  • 10 Hong A, Friedman JM. Synth. Commun. 1997; 27: 2971