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Synlett 2011(7): 947-950  
DOI: 10.1055/s-0030-1259725
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Pd-Catalyzed Asymmetric Hydrogenation of C=C Bond of α,β-Unsaturated Ketones

Duo-Sheng Wanga, Da-Wei Wanga, Yong-Gui Zhou*a,b
a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, P. R. of China
Fax: +86(411)84379220; e-Mail: ygzhou@dicp.ac.cn;
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China
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Publication History

Received 26 November 2010
Publication Date:
10 March 2011 (online)

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Abstract

Homogenous palladium-catalyzed asymmetric hydrogenation of C=C double bond of α,β-unsaturated ketones has been ­developed by using palladium(II) trifluoroacetate/(S)-7,7′-bis-[di(4-methoxyphenyl]phosphino)-1,1′-spirobiindane complex [Pd(OCOCF3)2-(S)-An-SDP] as the catalyst under ambient hydrogen pressure and room temperature with up to 89% ee.

Key words

palladium - hydrogenation - unsaturated ketones - SDP ligand

    References and Notes

  • 1a Blaser H.-U. Pugin B. Spindler F. Applied Homogeneous Catalysis with Organometallic Compounds  2nd ed., Chap. 3.3.1. Wiley-VCH; Weinheim: 2000. 
    Google Scholar
  • 1b Tang W. Zhang X. Chem. Rev.  2003,  103:  3029 
    Google Scholar
  • 1c Rylander PN. Catalytic Hydrogenation in Organic Synthesis   Academic Press; New York: 1979.  p.175 
    Google Scholar
  • 1d The Handbook of Homogeneous Hydrogenation   de Vries JG. Elsevier CJ. Wiley-VCH; Weinheim: 2007. 
    Google Scholar
  • For other work on Pd-catalyzed asymmetric hydrogenation, see:
  • 2a Abe H. Amii H. Uneyama K. Org. Lett.  2001,  3:  313 
    Google Scholar
  • 2b Nanayakkara P. Alper H. Chem. Commun.  2003,  2384 
    Google Scholar
  • 2c Suzuki A. Mae M. Amii H. Uneyama K. J. Org. Chem.  2004,  69:  5132 
    Google Scholar
  • 2d Yang Q. Shang G. Gao W. Deng J. Zhang X. Angew. Chem. Int. Ed.  2006,  45:  3832 
    Google Scholar
  • 2e Rubio-Perez L. Perez-Flores FJ. Sharma P. Velasco L. Cabrera A. Org. Lett.  2009,  11:  265 
    Google Scholar
  • 2f Goulioukina NS. Bondarenko GN. Bogdanov AV. Gavrilov KN. Beletskaya IP. Eur. J. Org. Chem.  2009,  510 
    Google Scholar
  • For our work on Pd-catalyzed asymmetric hydrogenation, see:
  • 3a Wang Y.-Q. Lu S.-M. Zhou Y.-G. Org. Lett.  2005,  7:  3235 
    Google Scholar
  • 3b Wang Y.-Q. Zhou Y.-G. Synlett  2006,  1189 
    Google Scholar
  • 3c Wang Y.-Q. Lu S.-M. Zhou Y.-G. J. Org. Chem.  2007,  72:  3729 
    Google Scholar
  • 3d Wang Y.-Q. Yu C.-B. Wang D.-W. Wang X.-B. Zhou Y.-G. Org. Lett.  2008,  10:  2071 
    Google Scholar
  • 3e Yu C.-B. Wang D.-W. Zhou Y.-G. J. Org. Chem.  2009,  74:  5633 
    Google Scholar
  • 3f Wang D.-S. Chen Q.-A. Li W. Yu C.-B. Zhou Y.-G. Zhang X. J. Am. Chem. Soc.  2010,  132:  8909 
    Google Scholar
  • 3g Chen M.-W. Duan Y. Chen Q.-A. Wang D.-S. Yu C.-B. Zhou Y.-G. Org. Lett.  2010,  12:  5075 
    Google Scholar
  • 3h Zhou X.-Y. Bao M. Zhou Y.-G. Adv. Synth. Catal.  2011,  353:  84 
    Google Scholar
  • Importance of compounds with stereogenic centers at the α- or β-position to a carbonyl group, see:
  • 4a Honwad VK. Rao AS. Tetrahedron  1964,  20:  2921 
    Google Scholar
  • 4b Sakai T. Hirose Y. Chem. Lett.  1973,  491 
    Google Scholar
  • 4c Black WC. Bayly C. Belley M. Chan CC. Charleson S. Denis D. Gauthier JY. Gordon R. Guay D. Kargman S. Lau CK. Leblac Y. Mancini L. Ouellet M. Percival D. Roy P. Skorey K. Tagari P. Vickers P. Wong W. Xu L. Prasit P. Bioorg. Med. Chem. Lett.  1996,  6:  725 
    Google Scholar
  • 4d Austin JF. MacMillan DWC. J. Am. Chem. Soc.  2002,  124:  1172 
    Google Scholar
  • 4e Sandan LA. Acc. Chem. Res.  2007,  40:  1309 
    Google Scholar
  • Catalytic asymmetric hydrogenation of C=O over C=C:
  • 5a Mashima K. Akutagawa T. Zhang XY. Takaya H. Taketomi T. Kumobayashi H. Akutagawa S. J. Organomet. Chem.  1992,  428:  213 
    Google Scholar
  • 5b Ohkuma T. Ooka H. Ikariya T. Noyori R. J. Am. Chem. Soc.  1995,  117:  10417 
    Google Scholar
  • 5c Ohkuma T. Ikehira H. Ikariya T. Noyori R. Synlett  1997,  467 
    Google Scholar
  • 5d Ohkuma T. Koizumi M. Doucet H. Pham T. Kozawa M. Murata K. Katayama E. Yokozawa T. Ikariya T. Noyori R. J. Am. Chem. Soc.  1998,  120:  13529 
    Google Scholar
  • 5e Burk MJ. Hems W. Herzberg D. Malan C. Zanotti-Gerosa A. Org. Lett.  2000,  2:  4173 
    Google Scholar
  • 5f Lindner E. Ghanem A. Warad I. Eichele K. Mayer HA. Schurig V. Tetrahedron: Asymmetry  2003,  14:  1045 
    Google Scholar
  • Homogenous hydrogenations of cyclic enones, see:
  • 6a Solodar J. J. Org. Chem.  1978,  43:  1787 
    Google Scholar
  • 6b Le Maux P. Simonneaux G. J. Organomet. Chem.  1983,  252:  C60 
    Google Scholar
  • 6c Le Maux P. Massonneau V. Simonneaux G. J. Organomet. Chem.  1985,  284:  101 
    Google Scholar
  • 6d Massonneau V. Lemaux P. Simonneaux G. Tetrahedron Lett.  1986,  27:  5497 
    Google Scholar
  • 6e Massonneau V. Lemaux P. Simonneaux G. J. Organomet. Chem.  1987,  327:  269 
    Google Scholar
  • 6f Ohta T. Miyake T. Seido N. Kumobayashi H. Takaya H. J. Org. Chem.  1995,  60:  357 
    Google Scholar
  • 6g Dobbs DA. Vanhessche KPM. Brazi E. Rautenstrauch V. Lenoir J.-Y. Genet J.-P. Wiles J. Bergens SH. Angew. Chem. Int. Ed.  2000,  39:  1992 
    Google Scholar
  • 6h Solodar J. J. Org. Chem.  2002,  43:  1787 
    Google Scholar
  • 6i Hilgraf R. Pfaltz A. Adv. Synth. Catal.  2005,  347:  61 
    Google Scholar
  • 6j Ohshima T. Tadaoka H. Hori K. Sayo N. Mashima K. Chem. Eur. J.  2008,  14:  2060 
    Google Scholar
  • 6k Scheuermann née Taylor CJ. Jaekel C. Adv. Synth. Catal.  2008,  350:  2708 
    Google Scholar
  • 6l Shimizu H. Nagano T. Sayo N. Saito T. Ohshima T. Mashima K. Synlett  2009,  3143 
    Google Scholar
  • For homogenous hydrogenations of linear enones, see:
  • 7a Lu SM. Bolm C. Chem. Eur. J.  2008,  14:  7513 
    Google Scholar
  • 7b Lu SM. Bolm C. Angew. Chem. Int. Ed.  2008,  47:  8920 
    Google Scholar
  • 7c Lu WJ. Chen YW. Hou XL. Angew. Chem. Int. Ed.  2008,  47:  10133 
    Google Scholar
  • 7d Lu WJ. Chen YW. Hou XL. Adv. Synth. Catal.  2010,  352:  103 
    Google Scholar
  • 8a Tshchiya Y. Hamashima Y. Sodeoka M. Org. Lett.  2006,  8:  4851 
    Google Scholar
  • 8b Monguchi D. Beemelmanns C. Hashizume D. Hamashima Y. Sodeoka M. J. Organomet. Chem.  2008,  693:  867 
    Google Scholar
  • Selected examples, see:
  • 9a Xie J.-H. Zhou Q.-L. Acc. Chem. Res.  2008,  41:  581 
    Google Scholar
  • 9b Xie J.-H. Wang L.-X. Fu Y. Zhu S.-F. Fan B.-M. Duan H.-F. Zhou Q.-L. J. Am. Chem. Soc.  2003,  125:  4404 
    Google Scholar
  • 9c Xie J.-H. Zhou Z.-T. Kong W.-L. Zhou Q.-L. J. Am. Chem. Soc.  2007,  129:  1868 
    Google Scholar
  • 9d Fan B.-M. Xie J.-H. Li S. Wang L.-X. Zhou Q.-L. Angew. Chem. Int. Ed.  2007,  46:  1275 
    Google Scholar
  • 9e Liu S. Xie J.-H. Wang L.-X. Zhou Q.-L. Angew. Chem. Int. Ed.  2007,  46:  7506 
    Google Scholar
  • 9f Xie J.-H. Liu S. Kong W.-L. Bai W.-J. Wang X.-C. Wang L.-X. Zhou Q.-L. J. Am. Chem. Soc.  2009,  131:  4222 
    Google Scholar
10

Typical Procedure for the Asymmetric Hydrogenation of β,β-Disubstituted Unsaturated Ketones (S)-An-SDP (4.2 mg, 0.006 mmol) and Pd(OCOCF3)2 (1.7 mg, 0.005 mmol) were placed in a dried Schlenk tube under nitrogen atmosphere, and degassed anhyd acetone was added. The mixture was stirred at r.t. for 1 h. The solvent was removed under vacuum to give the catalyst. To this catalyst was added substrate 1a (0.25 mmol) and dry TFE (2 mL) under a hydrogen atmosphere, then the mixture was stirred at r.t. After confirmation of consumption of substrate by GC, the hydrogen gas was slowly released from the reaction vessel. The ee was determined by HPLC after purification on silica gel using PE and EtOAc. ( S )-1,3-Diphenylbutan-1-one (2a)
Yield 95%, 86% ee; [α]D r.t. +0.70 (c 1.87, CHCl3). ¹H NMR (400 MHz, CDCl3): δ =1.36 (d, J = 6.9 Hz, 3 H), 3.21 (dd, J = 16.4, 8.2 Hz, 1 H), 3.32 (dd, J = 16.5, 5.8 Hz, 1 H), 3.49-3.58 (m, 1 H), 7.20-7.24 (m, 1 H), 7.28-7.36 (m, 4 H), 7.42-7.50 (m, 2 H), 7.53-7.56 (m, 1 H), 7.93-7.96 (m, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 22.1, 35.7, 47.2, 126.5, 127.0, 128.2, 128.5, 128.7, 133.1, 137.4, 146.7, 199.2. HPLC (AD-H, eluent: hexanes-i-PrOH = 95:5, detector: 230 nm, flow rate: 0.8 mL/min), t R1 (S) = 7.6 min (major); t R2 (R) = 8.7 min.