Science China Chemistry

, Volume 53, Issue 9, pp 1899–1906 | Cite as

Nickel-catalyzed enantioselective hydrovinylation of silyl-protected allylic alcohols: An efficient access to homoallylic alcohols with a chiral quaternary center

  • Qi Zhang
  • Shou-Fei Zhu
  • Yan Cai
  • Li-Xin Wang
  • Qi-Lin ZhouEmail author


Asymmetric hydrovinylation of silyl-protected allylic alcohols catalyzed by nickel complexes of chiral spiro phosphoramidite ligands was developed. A series of homoallylic alcohols with a chiral quaternary center were produced in high yields (up to 97%) and high enantioselectivities (up to 95% ee). The reaction provides an efficient method for preparing bifunctional compounds with a chiral quaternary carbon center.


asymmetric hydrovinylation chiral spiro phosphorus ligands functionalized olefins chiral quaternary center 


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  1. 1.
    Jolly PW, Wilke G. in Applied Homogeneous Catalysis with Organometallic Compounds, Vol. 2 (Eds. Cornils B, Herrmann WA.), New York: Wiley-VCH, 1996. 1024–1048Google Scholar
  2. 2.
    Goossen LJ. Asymmetric hydrovinylation: New perspectives through use of modular ligand systems. Angew Chem Int Ed, 2002, 41: 3775–3778CrossRefGoogle Scholar
  3. 3.
    RajanBabu TV. Asymmetric hydrovinylation reaction. Chem Rev, 2003, 103: 2845–2860CrossRefGoogle Scholar
  4. 4.
    Wilke G, Monkiewicz J. DOS 3 618 169, priority 30.05.1986; Chem. Abstr. 1988, 109: 6735Google Scholar
  5. 5.
    Park H, RajanBabu TV. Tunable ligands for asymmetric catalysis: Readily available carbohydrate-derived diarylphosphinites induce high selectivity in the hydrovinylation of styrene derivatives. J Am Chem Soc, 2002, 124: 734–735CrossRefGoogle Scholar
  6. 6.
    Franciò G, Faraone F, Leitner W. Highly enantioselective nickelcatalyzed hydrovinylation with chiral phosphoramidite ligands. J Am Chem Soc, 2002, 124: 736–737CrossRefGoogle Scholar
  7. 7.
    Zhang A, RajanBabu TV. Fine-tuning monophosphine ligands for enhanced enantioselectivity. Influence of chiral hemilabile pendant groups. Org Lett, 2004, 6: 1515–1517CrossRefGoogle Scholar
  8. 8.
    Smith CR, RajanBabu TV. Efficient, selective, and green: Catalyst tuning for highly enantioselective reactions of ethylene. Org Lett, 2008, 10: 1657–1659CrossRefGoogle Scholar
  9. 9.
    Shi W-J, Zhang Q, Xie J-H, Zhu S-F, Hou G-H, Zhou Q-L. Highly enantioselective hydrovinylation of α-alkyl vinylarenes. An approach to the construction of all-carbon quaternary stereocenters. J Am Chem Soc, 2006, 128: 2780–2781CrossRefGoogle Scholar
  10. 10.
    Zhang A, RajanBabu TV. All-carbon quaternary centers via catalytic asymmetric hydrovinylation. New approaches to the exocyclic side chain stereochemistry problem. J Am Chem Soc, 2006, 128: 5620–5621CrossRefGoogle Scholar
  11. 11.
    Kumareswaran R, Nandi M, RajanBabu TV. Hydrovinylation of norbornene. Ligand-dependent selectivity and asymmetric variations. Org Lett, 2003, 5: 4345–4348CrossRefGoogle Scholar
  12. 12.
    Zhang A, RajanBabu TV. Hydrovinylation of 1,3-dienes: A new protocol, an asymmetric variation, and a potential solution to the exocyclic side chain stereochemistry problem. J Am Chem Soc, 2006, 128: 54–55CrossRefGoogle Scholar
  13. 13.
    Saha B, Smith CR, RajanBabu TV. Ligand tuning in asymmetric hydrovinylation of 1,3-dienes: A stereoselective route to either steroid-C20(S) or -C20 (R) derivatives. J Am Chem Soc, 2008, 130: 9000–9005CrossRefGoogle Scholar
  14. 14.
    Zhang Q, Zhu S-F, Qiao X-C, Wang L-X, Zhou Q-L. Nickel-catalyzed highly selective hydrovinylation of α-ketals of vinylarenes. Adv Synth Catal, 2008, 350: 1507–1510CrossRefGoogle Scholar
  15. 15.
    Xie J-H, Zhou Q-L. Chiral diphosphine and monodentate phosphorous ligands on a spiro scaffold for transition-metal-catalyzed asymmetric reactions. Acc Chem Res, 2008, 41: 581–593CrossRefGoogle Scholar
  16. 16.
    Melone G, Vecchi A, Pagani G, Testa E. Tropine dl-α-methyltropate (methyltropine) and its optical antipodes. J Org Chem, 1960, 25: 859–861CrossRefGoogle Scholar
  17. 17.
    Wilke G. π-Allyl nickel compounds and their preparation. US3422128, 1969Google Scholar
  18. 18.
    Nishida H, Takada N, Yoshimura M, Sonoda T, Kobayashi H. Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. Highly lipophilic stable anionic agent for solvent-extraction cations. Bull Chem Soc Jpn, 1984, 57: 2600–2604CrossRefGoogle Scholar
  19. 19.
    Brookhart M, Grant B, Volpe AF Jr. [(3,5-(CF3)2C6H3)4B][H(OEt2)2]+: A convenient reagent for generation and stabilization of cationic, highly electrophilic organometallic complexes. Organometallics, 1992, 11: 3920–3922CrossRefGoogle Scholar
  20. 20.
    Zhou H, Wang W-H, Fu Y, Xie J-H, Shi W-J, Wang L-X, Zhou Q-L. Highly enantioselective copper-catalyzed conjugate addition of diethylzinc to enones using chiral spiro phosphoramidites as ligands. J Org Chem, 2003, 68: 1582–1584CrossRefGoogle Scholar
  21. 21.
    Shi W-J, Wang L-X, Fu Y, Zhu S-F, Zhou Q-L. Highly regioselective asymmetric copper-catalyzed allylic alkylation with dialkylzinc using monodentate chiral spiro phosphoramidite and phosphite ligands. Tetrahedron: Asymmetry, 2003, 14: 3867–3872CrossRefGoogle Scholar
  22. 22.
    Yang Y, Zhu S-F, Duan H-F, Zhou C-Y, Wang L-X, Zhou Q-L. Asymmetric reductive coupling of dienes and aldehydes catalyzed by nickel complexes of spiro phosphoramidites: Highly enantioselective synthesis of chiral bishomoallylic alcohols. J Am Chem Soc 2007, 129: 2248–2249CrossRefGoogle Scholar
  23. 23.
    Duboudin JG, Jousseaume B, Saux A. Reactifs de grignard vinyliques γ fonctionnels: I. Reactivite des organomagnesiens vis-a-vis d’alcools α acetyleniques en presence d’halogenures cuivreux. J Organomet Chem, 1979, 168: 1–11CrossRefGoogle Scholar
  24. 24.
    Barluenga J, Fañanás FJ, Sanz R, Marcos C, Ignacio J M. 2-Arylallyl as a new protecting group for amines, amides and alcohols. Chem Commun, 2005, 933-935Google Scholar
  25. 25.
    Tueting DR, Echavarren AM, Stille JK. Palladium catalyzed coupling of organostannanes with vinyl epoxides. Tetrahedron, 1989, 45: 979–992CrossRefGoogle Scholar
  26. 26.
    Fadel A, Canet JL, Salaün J. Asymmetric construction of quaternary carbons from chiral malonates: total synthesis of (+)-epilaurene and (−)-isolaurene. Tetrahedron: Asymmetry, 1993, 4: 27–30CrossRefGoogle Scholar
  27. 27.
    Fadel A, Vandromme L. Total synthesis of (−)-sporochnol A, the fish deterrent from a chiral malonate. Tetrahedron: Asymmetry, 1999, 10: 1153–1162CrossRefGoogle Scholar
  28. 28.
    Imao D, Itoi A, Yamazaki A, Shirakura M, Ohtoshi R, Ogata K, Ohmori Y, Ohta T, Ito Y. Easy access to esters with a benzylic quaternary carbon center from diallyl malonates by palladium-catalyzed decarboxylative allylation. J Org Chem, 2007, 72, 1652–1658CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag Berlin Heidelberg 2010

Authors and Affiliations

  • Qi Zhang
    • 1
  • Shou-Fei Zhu
    • 1
  • Yan Cai
    • 1
  • Li-Xin Wang
    • 1
  • Qi-Lin Zhou
    • 1
    Email author
  1. 1.State Key Laboratory and Institute of Elemento-organic ChemistryNankai UniversityTianjinChina

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