Download PDF
Synlett 2007(20): 3201-3205  
DOI: 10.1055/s-2007-992378
LETTER
© Georg Thieme Verlag Stuttgart · New York

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;
Further Information

Publication History

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

    Permissions and Reprints All articles of this category

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

  • 1 Backvall J.-E. Modern Oxidation Methods   Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • For recent works describing transition-metal-mediated cleavage with Os reagent, see:
  • 2a Ley SV. Ramarao C. Lee A. Ostergaard N. Smith SC. Shirley IM. Org. Lett.  2003,  5:  185 
    CrossrefPubMedGoogle Scholar
  • 2b Travis BR. Narayan RS. Borhan B. J. Am. Chem. Soc.  2002,  124:  3824 
    CrossrefPubMedGoogle Scholar
  • 2c With AuCl reagent, see: Xing D. Guan B. Cai G. Fang Z. Yang L. Shi Z. Org. Lett.  2006,  8:  693 
    CrossrefPubMedGoogle Scholar
  • 3 Murahashi S. Komiya N. In Ruthenium in Organic Synthesis   Murahashi S. Wiley-VCH; Weinheim: 2004.  p.65-69  
    Google Scholar
  • For recent typical examples, see:
  • 4a Kim W. Park I. Park J. Org. Lett.  2006,  8:  2543 
    CrossrefGoogle Scholar
  • 4b Zhan B. White MA. Sham T. Pincock JA. Doucet R. Rao KVR. Robertson KN. Cameron TS. J. Am. Chem. Soc.  2003,  125:  2195 
    CrossrefGoogle Scholar
  • 4c Cheung W. Yu W. Yip W. Zhu N. Che C. J. Org. Chem.  2002,  67:  7716 
    CrossrefGoogle Scholar
  • 4d Yamaguchi K. Mori K. Mizugaki T. Ebitani K. Kaneda K. J. Am. Chem. Soc.  2000,  122:  7144 ; and references cited therein
    CrossrefGoogle Scholar
  • 5 For an excellent work detailing control of the oxidation stage with immobilized Ru species, see: Ho C. Yu W. Che C. Angew. Chem. Int. Ed.  2004,  43:  3303 
    CrossrefGoogle Scholar
  • 6a Okumoto H. Katto H. Synlett  2003,  1521 
    CrossrefGoogle Scholar
  • 6b Fukusaki F. Takeno S. Takeshi Bamba T. Okumoto H. Katto H. Kajiyama S. Kobayashi A. Biosci., Biotechnol., Biochem.  2004,  68:  1988 
    CrossrefGoogle Scholar
  • 7 Tada M. Yamashita Y. Petrykin V. Osada M. Yoshida K. Kakihana M. Chem. Mater.  2002,  14:  2845 
    CrossrefGoogle Scholar
  • 8 Carlsen PHJ. Katsuki T. Martin VS. Sharpless KB. J. Org. Chem.  1981,  46:  3936 
    CrossrefGoogle Scholar
  • For oxidation using RuCl3 leading to aldehyde, see:
  • 9a Yang D. Zhang C. J. Org. Chem.  2001,  66:  4814 
    CrossrefPubMedGoogle Scholar
  • For oxidation using RuCl3 leading to diol, see:
  • 9b Tiwari P. Misra AK. J. Org. Chem.  2006,  71:  2911 
    CrossrefPubMedGoogle Scholar
  • 9c Plietker B. Niggemann M. J. Org. Chem.  2005,  70:  2402 
    CrossrefPubMedGoogle Scholar
  • 9d Plietker B. Niggemann M. Org. Lett.  2003,  5:  3353 
    CrossrefPubMedGoogle Scholar
  • 9e For oxidation using RuCl3 leading to acyloin, see: Plietker B. J. Org. Chem.  2004,  69:  8287 
    CrossrefPubMedGoogle Scholar
  • 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:
  • 10a Shing TKM. Wong WF. Ikeno T. Yamada T. Org. Lett.  2007,  9:  207 
    CrossrefPubMedGoogle Scholar
  • 10b Lievens SC. Molinski TF. J. Am. Chem. Soc.  2006,  128:  11764 
    CrossrefPubMedGoogle Scholar
  • 10c Prenner RH. Binder WH. Schmid W. Liebigs Ann. Chem.  1994,  73 
    CrossrefPubMedGoogle Scholar
  • 10d The acetate 15 was synthesized by reaction of the aldehyde 19 and allyl Grignard reagent, followed by acetylation as illustrated in Scheme 4. For preparation of the intermediate aldehyde 19, see ref. 10a and: Calinaud P. Gelas J. In Preparative Carbohydrate Chemistry   Hanessian S. Marcel Dekker; New York: 1996.  p.p15 
    CrossrefPubMedGoogle Scholar
  • 10e The diacetonide 17 is readily accessible from d-mannose: Shing TKM. Wong WF. Cheng HM. Kwok WS. So KH. Org. Lett.  2007,  9:  753 
    CrossrefPubMedGoogle Scholar
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.