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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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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.
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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.