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

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

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• 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.

• 15b

  Diol 1c is a commercial product¹⁸ and was used without purification.

• 15c

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

• 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:
• 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 
• 15f The alkene preceding diol 1f was prepared according to: Büchner IK. Metz P. Tetrahedron Lett.  2001,  42:  5381 
• 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 

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%.