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Synlett 2008(3): 347-350  
DOI: 10.1055/s-2008-1032056
LETTER
© Georg Thieme Verlag Stuttgart · New York

Aerobic Oxidation of Cyclopentane-1,2-diols to Cyclopentane-1,2-diones on Pt/C Catalyst

Indrek Reilea, Anne Pajua, Margus Eekb, Tõnis Pehkc, Margus Lopp*a
a Department of Chemistry, Faculty of Science, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia
Fax: +372(620)2828; e-Mail: lopp@chemnet.ee;
b Prosyntest Ltd, Akadeemia tee 15, 12618 Tallinn, Estonia
c National Institute of Chemical Physics and Biophysics, Akadeemia tee 23, 12618 Tallinn, Estonia
Further Information

Publication History

Received 5 October 2007
Publication Date:
16 January 2008 (online)

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Abstract

A new method for the aerobic oxidation of cyclopentane-1,2-diols to corresponding 1,2-diones using heterogeneous Pt/C catalyst in the presence of LiOH is described. Different functional groups tolerate the oxidation conditions. Yields of 1,2-diones up to 76% were achieved.

Key words

diols - ketones - heterogeneous catalysis - oxidation - platinum

    References and Notes

  • 1 Blackburn TF. Schwartz J. J. Chem. Soc., Chem. Commun.  1977,  157 
    CrossrefGoogle Scholar
  • 2a Nishimura T. Onoue T. Ohe K. Uemura S. J. Org. Chem.  1999,  64:  6750 
    CrossrefPubMedGoogle Scholar
  • 2b Hallmann K. Moberg C. Adv. Synth. Catal.  2001,  343:  260 
    CrossrefPubMedGoogle Scholar
  • 2c Schultz MJ. Park CC. Sigman MS. Chem. Commun.  2002,  3034 
    CrossrefPubMedGoogle Scholar
  • 2d Jensen DR. Schultz MJ. Mueller JA. Sigman MS. Angew. Chem. Int. Ed.  2003,  42:  3810 
    CrossrefPubMedGoogle Scholar
  • 2e Iwasava T. Tokunaga M. Obora Y. Tsuji Y. J. Am. Chem. Soc.  2004,  126:  6554 
    CrossrefPubMedGoogle Scholar
  • 2f Schultz MJ. Hamilton SS. Jensen DR. Sigman MS. J. Org. Chem.  2005,  70:  3343 
    CrossrefPubMedGoogle Scholar
  • 2g Steinhoff BA. King AE. Stahl SS. J. Org. Chem.  2006,  71:  1861 
    CrossrefPubMedGoogle Scholar
  • 3a ten Brink G.-J. Arends IWCE. Sheldon RA. Science  2000,  287:  1636 
    CrossrefGoogle Scholar
  • 3b Buffin BP. Clarkson JP. Belitz NL. Kundu A. J. Mol. Catal. A: Chem.  2005,  225:  111 
    CrossrefGoogle Scholar
  • 4a Jia C.-G. Jing F.-Y. Hu W.-D. Huang M.-Y. Jiang Y.-Y. J. Mol. Catal.  1994,  91:  139 
    CrossrefGoogle Scholar
  • 4b Stuchinskaya TL. Musawir M. Kozhevnikova EF. Kozhevnikov IV. J. Catal.  2005,  231:  41 
    CrossrefGoogle Scholar
  • 5a Karimi B. Abedi S. Clark JH. Budarin V. Angew. Chem. Int. Ed.  2006,  45:  4776 
    CrossrefGoogle Scholar
  • 5b Yamada YMA. Arakawa T. Hocke H. Uozumi Y. Angew. Chem. Int. Ed.  2007,  46:  704 
    CrossrefGoogle Scholar
  • 6a Kakiuchi N. Maeda Y. Nishimura T. Uemura S. J. Org. Chem.  2001,  66:  6620 
    CrossrefGoogle Scholar
  • 6b Yamaguchi K. Mizuno N. Chem. Eur. J.  2003,  9:  4353 
    CrossrefGoogle Scholar
  • 6c Karimi B. Zamani A. Clark JH. Organometallics  2005,  24:  4695 
    CrossrefGoogle Scholar
  • 7 Steele AM. Zhu J. Tsang SC. Catal. Lett.  2001,  73:  9 
    CrossrefGoogle Scholar
  • 8a Iwahama T. Sakaguchi S. Nishiyama Y. Ishii Y. Tetrahedron Lett.  1995,  36:  6923 
    CrossrefGoogle Scholar
  • 8b Iwahama T. Yoshino Y. Keitoku T. Sakaguci S. Ishii Y. J. Org. Chem.  2000,  65:  6502 
    CrossrefGoogle Scholar
  • 9a Paju A. Kanger T. Pehk T. Müürisepp A.-M. Lopp M. Tetrahedron: Asymmetry  2002,  13:  2439 
    CrossrefGoogle Scholar
  • 9b Paju A. Laos M. Jõgi A. Päri M. Jäälaid R. Pehk T. Kanger T. Lopp M. Tetrahedron Lett.  2006,  47:  4491 
    CrossrefGoogle Scholar
  • 10 Paju A. Kanger T. Pehk T. Eek M. Lopp M. Tetrahedron  2004,  60:  9081 
    CrossrefGoogle Scholar
  • 12a Perry RH. Green DW. Maloney JO. Perry’s Chemical Engineers’ Handbook, Seventh Edition   McGraw-Hill; New York: 1997. 
    CrossrefGoogle Scholar
  • 12b Steinhoff BA. Stahl SS. J. Am. Chem. Soc.  2006,  128:  4348 
    CrossrefGoogle Scholar
  • 13 Bäckvall J.-E. Modern Oxidation Methods   John Wiley and Sons; New York: 2004.  p.87 
    Google Scholar
  • 14 Mueller JA. Sigman MS. J. Am. Chem. Soc.  2003,  125:  7005 
    CrossrefPubMedGoogle Scholar
  • Preparation of Substrates
  • 15a

    Substrates 1a,b and 1d-f were prepared from the corresponding alkenes according to the following dihydroxylation procedure: Alkene was dissolved in a H2O-t-BuOH mixture (1:3), and NMO (1.3 equiv) and fiber bound OsO4 catalyst (0.1 mol%) were added. The reaction mixture was stirred at 60 °C for an appropriate time (the reaction was monitored by TLC), the catalyst filtered, rinsed with EtOAc, and the filtrate quenched with an aqueous solution of Na2S2O3 (10%). The aqueous layer was extracted with EtOAc, the organic extracts combined, dried over MgSO4, the solvent evaporated and the crude product purified by flash chromatography, to afford the corresponding diol. Due to the synthetic route always the cis-diol was obtained as two isomers at the 3-position and used as a mixture.
    CrossrefGoogle Scholar
  • 15b

    Diol 1c is a commercial product18 and was used without purification.
    CrossrefGoogle Scholar
  • 15c

    Alkenes preceding diols 1a and 1b were prepared from 2-cyclopentene-1-acetic acid.9a

    CrossrefGoogle Scholar
  • 15d Frei U, and Kirchmayr R. inventors; EP  0278914. The alkene preceding diol 1d was prepared from 2-cyclopentene-1-acetic acid ethyl ester by transesterification, as reported by:
    CrossrefGoogle Scholar
  • 15e Alkenes preceding diols 1e and 1g were prepared from 2-cyclo-pentene-1-acetic acid according to: Bertrand MB. Wolfe JP. Tetrahedron  2005,  61:  6447 
    CrossrefGoogle Scholar
  • 15f The alkene preceding diol 1f was prepared according to: Büchner IK. Metz P. Tetrahedron Lett.  2001,  42:  5381 
    CrossrefGoogle Scholar
  • 17 All products have been fully characterized by 1H NMR and 13C NMR. The analyses of known compounds are in agreement with published data. The characteristics of compounds are as follows:Compound 2a: 1H NMR (800 MHz, CDCl3): δ = 7.48 (m, 4 H, Bn o-, m-), 7.43 (m, 1 H, Bn p-), 4.67 and 4.65 (2d, J = 11.8 Hz, 2 H, Bn CH2O), 3.74 (dd, J = 1.8, 10.9 Hz, 1 H, H-2), 3.69 (td, J = 2 × 5.0, 9.6 Hz, 1 H, H-7), 3.65 (ddd, J = 4.5, 8.5, 9.6 Hz, 1 H, H-7), 2.41 (ddddd, J = 0.6, 1.4, 1.9, 9.2, 19.6 Hz, 1 H, H-5), 2.20 (dddd, J = 0.4, 9.6, 11.0, 19.6 Hz, 1 H, H-5), 2.09 (ddddd, J = 0.5, 1.4, 6.2, 9.6, 13.1 Hz, 1 H, H-4), 1.97 (m, 2 H, H-3,6), 1.86 (m, 1 H, H-6), 1.51 (dddd, J = 9.1, 11.0, 11.6, 13.1 Hz, 1 H, H-4). 13C NMR (125 MHz, CDCl3): δ = 216.4 (C-1), 137.6 (C-9), 128.3 (C-11), 127.7 (C-10, C-12), 81.1 (C-2),73.1 (C-8), 68.9 (C-7), 42.5 (C-3), 34.2 (C-6), 34.0 (C-5), 23.3 (C-4). This structure was confirmed by 2D FT correlation diagrams and 1H-1H coupling constants from H-2 and H-5 (19.6 Hz geminal coupling). The assignment of trans-configuration results from the comparison of 13C chemical shifts with cis- and and trans-isomers of 3-[2-(benzyloxy)ethyl]cyclopentane-cis-1,2-diol.Compound 2a′: 1H NMR (500 MHz, CDCl3): δ = 7.28-7.34 (m, 5 H, Bn o-, m-, p-), 4.46 (s, 2 H, H-8), 4.01 (tdd, J = 2 × 0.5, 8.3, 11.8 Hz, 1 H, H-5), 3.57 and 3.54 (m, 2 H, H-7), 2.37 and 1.60 (m, 2 H, H-4), 2.30 (m, 1 H, H-2), 2.15 and 1.49 (m, 2 H, H-3), 2.02 and 1.75 (m, 2 H, H-6). 13C NMR (125 MHz, CDCl3): δ = 219.6 (C-1), 138.1 (C-9), 128.2 (C-11), 127.4 (C-10, C-12), 75.5 (C-5), 72.7 (C-8), 67.3 (C-7), 43.3 (C-2), 30.2 (C-6), 29.3 (C-4), 22.9 (C-3). Large coupling constants of C-5 carbinol proton point to a methylene group bonded to C-5.Compound 3a: data available in ref. 9a. Compound 3b: data available in ref. 9a. Compound 3c: data are in accordance with commercial compound purchased from Aldrich.Compound 3d: 1H NMR (500 MHz, CDCl3): δ = 6.85 (s, 1 H, OH), 3.38 (s, 2 H, CH2CO), 2.53 (m, 2 H, H-5), 2.43 (m, 2 H, H-4), 1.75 (q, J = 7.3 Hz, 2 H, CH 2CH3), 1.42 (s, 6 H, (CH3)2, 0.86 (t, J = 7.3 Hz, 3 H, CH2CH 3). 13C NMR (125 MHz, CDCl3): δ = 203.16 (C-3), 168.80 (COO), 150.04 (C-2), 138.61 (C-1), 84.24 [OC(Me)2], 35.42 (CH2CO), 33.36 (CH2CH3), 32.01 (C-4), 25.36 [OCMe 2 and C-5], 8.09 (CH3CH2). IR: ν = 3315, 2979, 2937, 2885, 1727, 1699, 1665, 1465, 1386, 1193, 1149 cm-1.Compound 3e: 1H NMR [500 MHz, CDCl3, broadened spectrum (E/Z exchange of Boc)]: δ = 6.40 (br s, 1 H, OH), 4.89 (br s, 1 H, NH), 3.41 (br m, 2 H, H-7), 2.59 (t, J = 2 × 6.6 Hz, 2 H, H-6), 2.47 (br m, 2 H, H-5), 2.41 (br m, 2 H, H-4), 1.41 (br s, 9 H, H-11). 13C NMR (125 MHz, CDCl3): δ = 203.21 (C-3), 155.96 (C-9), 149.57 (C-2), 144.18 (C-1), 79.33 (C-10), 37.82 (C-7), 31.90 (C-4), 29.88 (C-6), 28.32 (C-11), 25.51 (C-5). IR: ν = 3371, 3326, 3008, 1689, 1657, 1524, 1451, 1393, 1367, 1249, 1169, 1119 cm-1.Compound 3f: Ramage R. Griffiths GJ. Shutt FE. J. Chem. Soc., Perkin Trans. 1  1984,  7:  1531 
    Google Scholar
11

Johnson Matthey, 5% Platinum Charcoal Catalyst Type 160, 57.9% H2O.

16

General Procedure for the Catalytic Aerobic Oxidation of DiolsDiol (0.424 mmol), catalyst (5 mol%), LiOH·H2O (1.0 equiv) and solvent [2 mL, MeCN-H2O (1:1)] were added to a 10 mL glass reactor, equipped with a condenser and stirred at 60 °C for an appropriate time. Consumption of the substrate was monitored by TLC. When the substrate was consumed the catalyst was filtered, rinsed with EtOAc (15 mL), EtOAc (10 mL) was added and the obtained two-phase solution was washed with 0.025 M HCl aq soln (20 mL). The separated aqueous layer was extracted once with EtOAc (20 mL). The combined extracts were dried over MgSO4 and concentrated in vacuum. The solid crude product was purified by flash chromatography [EtOAc-PE (2.5:10)] to give the diketone as a white crystalline solid.

18

3-Methylcyclopentane-1,2-diol was purchased from Alfa Aesar as a mixture of diastereomers, 95%.