Use of the Composite Material RuO2/BaTi4O9 as an Environmentally Benign Solid Catalyst for the Oxidative Cleavage of Olefins

Hiroshi Okumoto; Kazuhiro Ohtsuka; Shinji Banjoya

doi:10.1055/s-2007-992378

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Synlett 2007(20): 3201-3205
DOI: 10.1055/s-2007-992378

LETTER

Use of the Composite Material RuO₂/BaTi₄O₉ as an Environmentally Benign Solid Catalyst for the Oxidative Cleavage of Olefins

Hiroshi Okumoto*, Kazuhiro Ohtsuka, Shinji Banjoya
Department of Life Science, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajima, Kurashiki, 712-8505 Japan
Fax: +81(86)4401062; e-Mail: okmt@chem.kusa.ac.jp;

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Publication History

Received 11 September 2007
Publication Date:
21 November 2007 (online)

Abstract
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Abstract

Catalytic use of a composite material, RuO₂/BaTi₄O₉, in combination with NaIO₄ in EtOAc-H₂O has been shown to efficiently cleave alkenes, affording ketones, aldehydes and/or carboxylic acids in high yields.

Key words

ruthenium - green chemistry - oxidation - cleavage - heterogeneous catalysis

References and Notes

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The sugar derivatives 8, 11 and 13 were prepared from d-ribose, d-arabinose and d-xylose, respectively, according to the literature, followed by usual acetylation:
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11

General Experimental Procedure: To a solution of olefin (0.5 mmol) in EtOAc (3 mL), H₂O (5 mL) and phosphate buffer (pH 6.88, 1 mL) were added 3% RuO₂/BaTi₄O₉ (10 mg) and then NaIO₄ (3 mmol) at r.t. The reaction mixture was stirred for the indicated times. Solids were filtered and washed with H₂O. Filtrates were extracted with EtOAc and the organic layer was dried and concentrated. The residue was then chromatographed on silica gel to give the product.

12

2a: ¹H NMR (300 MHz, CDCl₃): δ = 0.85 (t, J = 7.6 Hz, 3 H), 1.25 (t, J = 7.2 Hz, 6 H), 2.05 (q, J = 7.6 Hz, 2 H), 2.17 (s, 3 H), 3.10 (s, 2 H), 4.19 (q, J = 7.0 Hz, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 8.8, 13.7, 26.2, 30.0, 45.2, 55.6, 61.1, 170.5, 204.9.
2b: a mixture of separable diastereomers in a ratio of ca. 4:1. Major product: ¹H NMR (500 MHz, CDCl₃): δ = 1.04 (d, J = 6.4 Hz, 3 H), 1.43 (ddd, J = 3.3, 13.1, 26.3 Hz, 1 H), 1.73 (ddd, J = 3.4, 13.1, 25.6 Hz, 1 H), 2.19 (s, 3 H), 2.08-2.25 (m, 2 H), 2.35-2.45 (m, 1 H), 2.45-2.52 (m, 2 H), 2.77-2.86 (m, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 14.2, 27.7, 28.2, 34.5, 42.6, 44.5, 52.1, 208.1, 211.4. Minor product: ¹H NMR (500 MHz, CDCl₃): δ = 1.09 (d, J = 7.0 Hz, 3 H), 1.50-1.58 (m, 1 H), 1.91-2.10 (m, 3 H), 2.18 (s, 3 H), 2.30-2.42 (m, 2 H), 2.65 (ddd, J = 1.2, 6.1, 15.0 Hz, 1 H), 3.06-3.12 (m, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 15.2, 24.8, 28.1, 30.9, 40.5, 44.2, 50.1, 209.2, 211.3.
2c: ¹H NMR (500 MHz CDCl₃): δ = 1.42 (s, 3 H), 2.00 (ddd, J = 1.2, 11.0, 14.9 Hz, 1 H), 2.19 (s, 3 H), 2.25 (dd, J = 11.0, 18.0 Hz, 1 H), 2.51 (dt, J = 3.0, 14.9 Hz, 1 H), 2.63 (ddd, J = 1.2, 4.9, 18.0 Hz, 1 H), 3.10-3.18 (m, 1 H), 3.48 (dd, J = 0.9, 3.0 Hz, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 15.1, 25.8, 28.2, 37.5, 41.8, 59.0, 60.6, 203.8, 208.2.
2d: ¹H NMR (500 MHz, CDCl₃): δ = -0.29 (s, 3 H), -0.10 (s, 3 H), 0.73 (s, 9 H), 2.03 (s, 3 H), 2.42 (dd, J = 4.3, 14.6 Hz, 1 H), 2.81 (dd, J = 8.8, 14.6 Hz, 1 H), 3.68 (s, 3 H), 5.00 (dd, J = 4.3, 8.8 Hz, 1 H), 6.74 (d, J = 8.3 Hz, 2 H), 7.14 (d, J = 8.3 Hz, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = -5.3, -4.7, 18.0, 25.7, 31.8, 54.4, 55.2, 71.6, 113.6, 126.9, 136.6, 158.8, 207.3.
2e: ¹H NMR (500 MHz, CDCl₃): δ = 1.40-1.80 (m, 6 H), 2.12, 2.20 (s, 3 H), 2.60-2.70 (m, 1 H), 3.00-3.10 (m, 1 H), 3.20-3.30 (m, 0.5 H), 3.40-3.60 (m, 1 H), 3.78 (s, 3 H), 3.70-3.90 (m, 0.5 H), 4.39, 4.84 (t, J = 3.3 Hz, 1 H), 5.01 (dd, J = 4.6, 8.5 Hz, 0.5 H), 5.14 (dd, J = 4.9, 8.9 Hz, 0.5 H), 6.80-6.90 (m, 2 H), 7.25-7.35 (m, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = 19.1, 19.1, 25.2, 30.4, 31.0, 31.0, 51.4, 51.6, 55.0, 55.1, 61.9, 62.0, 72.7, 75.2, 94.5, 98.9, 113.5, 113.8, 127.4, 128.0, 132.7, 134.6, 158.7, 159.2, 206.6.
2f: ¹H NMR (300 MHz, CDCl₃): δ = 1.10 (t, J = 7.05 Hz, 3 H), 2.15 (s, 3 H), 3.20-3.45 (m, 2 H), 3.65 (s, 1.5 H), 3.72 (s, 1.5 H), 3.98, 4.04 (s, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = 12.9, 13.3, 26.5, 26.7, 42.8, 43.4, 52.5, 52.6, 56.3, 56.6, 156.1, 156.8, 204.0, 204.1.
2g: ¹H NMR (300 MHz, CDCl₃): δ = 2.03 (s, 1.5 H), 2.06 (s, 1.5 H), 3.71 (s, 1.5 H), 3.77 (s, 1.5 H), 3.90 (s, 1 H), 3.99 (s, 1 H), 4.52 (s, 1 H), 4.54 (s, 1 H), 7.15-7.40 (m, 5 H). ¹³C NMR (126 MHz): δ = 26.6, 26.8, 51.0, 51.5, 52.9, 52.9, 55.4, 55.7, 127.4, 127.5, 128.0, 128.5, 128.5, 136.7, 156.8, 157.0, 203.5, 203.6.
2h: ¹H NMR (300 MHz, CDCl₃): δ = 1.90 (s, 1.5 H), 1.92 (s, 1.5 H), 2.15 (s, 1.5 H), 2.16 (s, 1.5 H), 4.43 (s, 1 H), 4.44 (s, 1 H), 7.25-7.50 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.8, 26.9, 59.1, 127.6, 127.9, 129.6, 143.3, 170.5, 202.3.
4: ¹H NMR (500 MHz, CDCl₃): δ = 1.35-1.47 (m, 1 H), 1.44 (s, 3 H), 1.53 (s, 3 H), 1.82-1.90 (m, 1 H), 1.95 (s, 3 H), 2.16 (s, 3 H), 2.15-2.23 (m, 1 H), 2.31-2.37 (m, 1 H), 2.48-2.59 (m, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 22.2, 22.3, 24.0, 24.3, 30.1, 35.0, 42.0, 43.9, 84.4, 170.3, 179.0, 208.3.
6a: ¹H NMR (500 MHz, CDCl₃): δ = 1.80-2.02 (m, 2 H), 2.067 (s, 3 H), 2.071 (s, 3 H), 2.54 (t, J = 7.1 Hz, 2 H), 4.06 (dd, J = 6.1, 11.9 Hz, 1 H), 4.24 (dd, J = 3.7, 11.9 Hz, 1 H), 5.05-5.20 (m, 1 H), 9.77 (s, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 20.6, 20.8, 23.1, 39.4, 64.6, 70.5, 170.4, 170.6, 200.6.
7a: ¹H NMR (500 MHz, CDCl₃): δ = 1.90-2.00 (m, 2 H), 2.07 (s, 6 H), 2.43 (dt, J = 1.5, 7.6 Hz, 2 H), 4.06 (dd, J = 5.9, 11.9 Hz, 1 H), 4.25 (dd, J = 3.7, 11.9 Hz, 1 H), 5.09-5.20 (m, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 20.7, 20.9, 25.8, 29.7, 64.7, 70.4, 170.6, 170.8, 178.1.
6b: ¹H NMR (500 MHz, CDCl₃): δ = 1.27 (t, J = 7.0 Hz, 3 H), 1.52 (s, 3 H), 2.26 (s, 3 H), 2.90 (d, J = 17.7 Hz, 1 H), 3.00 (d, J = 17.7 Hz, 1 H), 4.22 (q, J = 7.0 Hz, 2 H), 9.71 (s, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 13.8, 20.4, 26.0, 39.4, 48.5, 56.9, 61.9, 171.6, 199.1, 204.7.
7b: ¹H NMR (500 MHz, CDCl₃): δ = 1.27 (t, J = 7.0 Hz, 3 H), 1.51 (br s, 3 H), 2.23 (br s, 3 H), 2.92 (br s, 2 H), 4.21 (q, J = 7.0 Hz, 2 H), 9.5 (br, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 13.8, 39.4, 61.8, 171.6.
6c: ¹H NMR (300 MHz, CDCl₃): δ = 1.42 (s, 4.5 H), 1.45 (s, 4.5 H), 2.85-3.25 (m, 2 H), 3.69 (s, 1.5 H), 3.71 (s, 1.5 H), 3.75 (s, 1.5 H), 3.76 (s, 1.5 H), 3.90-4.25 (m, 2 H), 4.45-4.52 (m, 0.5 H), 4.80-4.90 (m, 0.5 H), 9.56 (m, 0.5 H), 9.58 (s, 0.5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 28.3, 35.5, 52.1, 57.4, 57.5, 58.6, 58.6, 58.7, 58.7, 81.9, 99.2, 157.8, 154.8, 170.7, 170.7, 170.8, 170.8, 171.5, 171.5, 171.6, 171.6, 171.6, 171.9, 199.0.
7c: ¹H NMR (500 MHz, CDCl₃): δ = 1.43 (s, 4.5 H), 1.44 (s, 4.5 H), 2.90-3.20 (m, 2 H), 3.69 (s, 1.5 H), 3.70 (s, 1.5 H), 3.75 (s, 1.5 H), 3.76 (s, 1.5 H), 3.95-4.11 (m, 1.5 H), 4.32 (d, J = 18.4 Hz, 0.5 H), 4.53 (t, J = 6.4 Hz, 0.5 H), 4.80 (t, J = 6.4 Hz, 0.5 H), 6.35 (br, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 27.9, 28.1, 34.9, 35.8, 49.8, 50.4, 52.0, 52.6, 52.9, 57.1, 58.3, 60.4, 82.0, 82.2, 154.3, 170.9, 171.5, 171.7, 171.7, 173.5, 173.7.
6d: ¹H NMR (500 MHz, CDCl₃): δ = 1.44 (s, 9 H), 4.33 (s, 2 H), 7.20-7.40 (m, 5 H), 9.70 (s, 1 H). ¹³C NMR (126 MHz): δ = 28.2, 60.1, 81.5, 126.4, 128.9, 142.5, 198.1.
7d: ¹H NMR (500 MHz, CDCl₃): δ = 1.42 (s, 9 H), 4.30 (s, 2 H), 6.00 (br, 1 H), 7.20-7.40 (m, 5 H). ¹³C NMR (126 MHz, CDCl₃): δ = 28.1, 52.2, 81.3, 126.3, 128.7, 142.5, 154.9, 175.2.
7e: ¹H NMR (300 MHz, CDCl₃): δ = 4.30-5.00 (br, 1 H), 4.68 (s, 2 H), 6.90-7.40 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 64.8, 72.6, 114.7, 122.1, 129.6, 157.4. 174.3.
9: ¹H NMR (500 MHz, CDCl₃): δ = 1.35 (s, 3 H), 1.40 (s, 9 H), 2.11 (s, 3 H), 2.65-2.82 (m, 2 H), 3.87-3.94 (m, 2 H), 4.05-4.09 (m, 1 H), 4.25-4.30 (m, 1 H), 4.48-4.54 (m, 1 H), 5.16-5.21 (m, 1 H), 9.81 (s, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 20.9, 25.3, 26.4, 26.7, 27.1, 47.0, 66.1, 71.7, 72.4, 74.0, 79.5, 109.6, 110.1, 170.0, 199.4.
10: ¹H NMR (500 MHz, CDCl₃): δ = 1.35 (s, 3 H), 1.40 (s, 9 H), 2.11 (s, 3 H), 2.63 (dd, J = 8.5, 16.1 Hz, 1 H), 2.76 (dd, J = 3.5, 16.1 Hz, 1 H), 3.88-3.96 (m, 2 H), 4.08 (dd, J = 6.4, 8.3 Hz, 1 H), 4.29 (dd, J = 6.4, 11.9 Hz, 1 H), 4.45 (dt, J = 3.6, 8.3 Hz, 1 H), 5.22 (t, J = 5.0 Hz, 1 H), 5.90-6.20 (br, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 21.1, 25.5, 26.5, 27.0, 27.3, 38.9, 66.2, 72.0, 74.1, 74.3, 79.5, 109.8, 110.4, 170.3, 175.6.
12: ¹H NMR (500 MHz, CDCl₃): δ = 1.36 (s, 3 H), 1.40 (s, 6 H), 1.41 (s, 3 H), 2.14 (s, 3 H), 2.58-2.78 (m, 2 H), 3.82-3.92 (m, 1 H), 3.95-4.10 (m, 2 H), 4.10-4.20 (m, 1 H), 4.25-4.33 (m, 1 H), 5.08-5.11 (m, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 20.8, 25.3, 26.5, 26.5, 27.3, 37.5, 66.1, 70.2, 72.8, 75.0, 79.3, 109.5, 109.7, 170.4, 174.6.
14: ¹H NMR (500 MHz, CDCl₃): δ = 2.05 (s, 3 H), 2.102 (s, 3 H), 2.104 (s, 3 H), 2.11 (s, 6 H), 2.63 (dd, J = 6.1, 16.8 Hz, 1 H), 2.69 (dd, J = 6.1, 16.8 Hz, 1 H), 4.03 (dd, J = 6.1, 11.9 Hz, 1 H), 4.27 (dd, J = 4.3, 11.9 Hz, 1 H), 5.30-5.45 (m, 4 H). ¹³C NMR (126 MHz, CDCl₃): δ = 20.5, 20.5, 20.6, 20.6, 20.7, 35.0, 61.8, 67.8, 68.9, 69.0, 70.4, 169.8, 170.0, 170.0, 170.2, 170.5, 173.7.
16: 2:1 mixture of diastereomers. ¹H NMR (500 MHz, CDCl₃): δ = 1.33, 1.36, 1.37, 1.38 (s, 12 H), 2.03, 2.04 (s, 3 H), 2.60-2.85 (m, 2 H), 3.75-3.93 (m, 2 H), 3.96-4.20 (m, 3 H), 5.25-5.40 (m, 1 H), 6.50 (br, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 20.8, 20.9, 25.4, 25.4, 26.0, 26.1, 26.6, 26.9, 27.0, 27.0, 35.4, 35.9, 65.5, 65.6, 67.5, 70.3, 74.6, 75.4, 76.1, 77.5, 77.6, 78.4, 109.8, 109.8, 110.0, 110.5, 170.3, 170.4, 174.8, 175.0.
18: 3:2 mixture of diastereomers. ¹H NMR (500 MHz, CDCl₃): δ = 1.35, 1.36, 1.38, 1.44, 1.49, 1.51 (s, 12 H), 2.05, 2.06, 2.09, 2.10, 2.11 (s, 6 H), 2.60-2.90 (m, 2 H), 3.75-4.45 (m, 5 H), 5.00-5.50 (m, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = 20.8, 20.9, 21.0, 25.1, 25.3, 25.4, 25.6, 26.0, 26.3, 26.3, 36.2, 36.4, 65.9, 67.1, 67.9, 69.3, 69.5, 70.2, 75.3, 75.4, 75.8, 76.5, 76.6, 76.9, 109.0, 109.2, 110.2, 169.9, 170.0, 170.2, 170.4, 174.4, 174.9.