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

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. 
• 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 
• 2b Travis BR. Narayan RS. Borhan B. J. Am. Chem. Soc.  2002,  124:  3824 
• 2c With AuCl reagent, see: Xing D. Guan B. Cai G. Fang Z. Yang L. Shi Z. Org. Lett.  2006,  8:  693 
• 3 Murahashi S. Komiya N. In Ruthenium in Organic Synthesis   Murahashi S. Wiley-VCH; Weinheim: 2004.  p.65-69  
• For recent typical examples, see:
• 4a Kim W. Park I. Park J. Org. Lett.  2006,  8:  2543 
• 4b Zhan B. White MA. Sham T. Pincock JA. Doucet R. Rao KVR. Robertson KN. Cameron TS. J. Am. Chem. Soc.  2003,  125:  2195 
• 4c Cheung W. Yu W. Yip W. Zhu N. Che C. J. Org. Chem.  2002,  67:  7716 
• 4d Yamaguchi K. Mori K. Mizugaki T. Ebitani K. Kaneda K. J. Am. Chem. Soc.  2000,  122:  7144 ; and references cited therein
• 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 
• 6a Okumoto H. Katto H. Synlett  2003,  1521 
• 6b Fukusaki F. Takeno S. Takeshi Bamba T. Okumoto H. Katto H. Kajiyama S. Kobayashi A. Biosci., Biotechnol., Biochem.  2004,  68:  1988 
• 7 Tada M. Yamashita Y. Petrykin V. Osada M. Yoshida K. Kakihana M. Chem. Mater.  2002,  14:  2845 
• 8 Carlsen PHJ. Katsuki T. Martin VS. Sharpless KB. J. Org. Chem.  1981,  46:  3936 
• For oxidation using RuCl₃ leading to aldehyde, see:
• 9a Yang D. Zhang C. J. Org. Chem.  2001,  66:  4814 
• For oxidation using RuCl₃ leading to diol, see:
• 9b Tiwari P. Misra AK. J. Org. Chem.  2006,  71:  2911 
• 9c Plietker B. Niggemann M. J. Org. Chem.  2005,  70:  2402 
• 9d Plietker B. Niggemann M. Org. Lett.  2003,  5:  3353 
• 9e For oxidation using RuCl₃ leading to acyloin, see: Plietker B. J. Org. Chem.  2004,  69:  8287 
• 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 
• 10b Lievens SC. Molinski TF. J. Am. Chem. Soc.  2006,  128:  11764 
• 10c Prenner RH. Binder WH. Schmid W. Liebigs Ann. Chem.  1994,  73 
• 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 
• 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 

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.