Nitrosyl Tetrafluoroborate Catalyzed Preparation of 2,3-Unsaturated Glycosides and 2-Deoxyglycosides of Hindered Alcohols, Thiols, and Sulfonamides

Abstract

Nitrosyl tetrafluoroborate (NOBF₄) has been successfully applied as an efficient organocatalyst for the preparation of 2,3-unsaturated and 2-deoxyglycosides of hindered alcohols, aryl thiols, and aryl sulfonamides from glycal derivatives under the Ferrier rearrangement conditions. Product yields and stereo-outcomes were very good.

Key words

glycal - Ferrier rearrangement - NOBF₄ - 2,3-unsaturated glycoside - 2-deoxyglycoside

• References and Notes

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• 45 Spectral data of the products those are not reported earlier are as follows. 5-Methyl-2-hexyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (4) ¹H NMR (500 MHz, CDCl₃): δ = 5.78–5.71 (m, 1 H, H-2), 5.69–5.66 (m, 1 H, H-3), 5.23–5.20 (m, 1 H, H-4), 5.05 (br s, 1 H, H-1), 4.19–4.10 (m, 2 H, H-6_ab), 4.02–3.98 (m, 1 H), 1.99, 1.96 (2 s, 6 H, 2 COCH₃), 1.72–1.58 (m, 1 H), 1.48–1.38 (m, 2 H), 1.18 (br s, 3 H), 1.13–1.07 (m, 2 H), 0.89, 0.84 (2 s, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 170.7, 170.2, 129.0, 128.4, 91.2, 67.1, 65.2, 63.4, 47.5, 25.0, 23.1, 23.0, 22.9, 22.5, 21.0, 20.8, 20.1. ESI-MS: m/z = 351.1 [M + Na]⁺. Anal. Calcd for C₁₇H₂₈O₆ (328.18): C, 62.17; H, 8.59. Found: C, 62.02; H, 8.80. Cholesteryl 3,4,6-Tri-O-acetyl-2-deoxy-α-d-galactopyranoside (16) ¹H NMR (500 MHz, CDCl₃): δ = 5.28–5.23 (m, 2 H, H-1, H-3), 5.08 (br s, 1 H, H-4), 4.17–4.15 (m, 1 H, H-5), 4.04–3.97 (m, 2 H, H-6_ab), 3.40–3.30 (m, 1 H), 2.26–2.21 (m, 1 H), 2.16 (s, 3 H, COCH₃), 2.03–1.98 (m, 1 H, H-2_e), 1.97, 1.90 (2 s, 6 H, 2 COCH₃), 1.92–1.86 (m, 1 H, H-2_a), 1.80–0.60 (m, 43 H, cholesterol). ¹³C NMR (125 MHz, CDCl₃): δ = 170.4, 170.1, 170.0, 140.7, 121.9, 95.7, 77.3, 66.9, 66.7, 66.4, 62.7, 56.7, 56.1, 50.2, 42.3, 40.0, 39.8, 39.5, 37.1, 36.7, 36.2, 35.8, 31.9, 31.8, 30.7, 28.2, 28.0, 27.9, 24.3, 23.8, 22.8, 22.6, 21.0, 20.9, 20.8, 20.7, 19.3, 18.7, 11.8. ESI-MS: m/z = 681.4 [M + Na]⁺. Anal. Calcd for C₃₉H₆₂O₈ (658.44): C, 71.09; H, 9.48. Found: C, 70.91; H, 9.66. Benzenesulfonamido 3,4,6-Tri-O-acetyl-2-deoxy-α-d-galactopyranoside (17) ¹H NMR (500 MHz, CDCl₃): δ = 7.86–7.82 (m, 2 H, ArH), 7.51–7.40 (m, 2 H, ArH), 6.70 (d, J = 7.5 Hz, 1 H, NH), 5.45–5.43 (m, 1 H, H-1), 5.19–5.15 (m, 1 H, H-3), 5.11 (br s, 1 H, H-4), 3.71–3.67 (m, 1 H, H-6_a), 3.62–3.59 (m, 1 H, H-6_b), 3.14–3.12 (m, 1 H, H-5), 2.25–2.19 (m, 1 H, H-2_e), 2.00, 1.98, 1.78 (3 s, 9 H, 3 COCH₃), 1.80–1.74 (m, 1 H, H-2_a). ¹³C NMR (125 MHz, CDCl₃): δ = 171.2, 170.2, 170.1, 141.1-126.7 (ArC), 79.1, 66.7, 65.7, 65.5, 60.8, 29.3, 20.8, 20.7, 20.6. ESI-MS: m/z = 452.1 [M + Na]⁺. Anal. Calcd for C₁₈H₂₃NO₆S (429.11): C, 50.34; H, 5.40. Found: C, 50.26; H, 5.57. p-Toluenesulfonamido 3,4,6-Tri-O-acetyl-2-deoxy-β-d-galactopyranoside (18) ¹H NMR (500 MHz, CDCl₃): δ = 7.71–7.69 (m, 2 H, ArH), 7.21–7.17 (m, 2 H, ArH), 6.28 (d, J = 7.6 Hz, 1 H, NH), 5.12 (d, J = 3.0 Hz, 1 H, H-4), 4.94–4.89 (m, 1 H, H-3), 4.86–4.81 (m, 1 H, H-1), 3.84–3.80 (m, 1 H, H-5), 3.71–3.63 (m, 1 H, H-6_ab), 2.32 (s, 3 H, CH₃), 1.99, 1.94, 1.91 (3 s, 9 H, 3 COCH₃), 1.98–1.95 (m, 1 H, H-2_e), 1.79–1.72 (m, J = 12.0 Hz each, 1 H, H-2_a). ¹³C NMR (125 MHz, CDCl₃): δ = 170.3, 170.2, 169.8, 143.8–127.2 (ArC), 80.6, 72.3, 68.5, 64.9, 61.3, 31.9, 21.5, 20.8, 20.7, 20.5. ESI-MS: m/z = 466.1 [M + Na]⁺. Anal. Calcd for C₁₉H₂₅NO₉S (443.12): C, 51.46; H, 5.68. Found: C, 51.32; H, 5.87. 2-Naphthyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (19) ¹H NMR (200 MHz, CDCl₃): δ = 7.96–7.42 (m, 7 H, ArH), 5.91–5.88 (m, 1 H, H-1), 5.39 (br s, 1 H, H-4), 5.36–5.29 (m, 1 H, H-3), 4.74–4.70 (m, 1 H, H-5), 4.15–4.04 (m, 2 H, H-6_ab), 2.58–2.47 (m, 1 H, H-2_e), 2.13 (s, 3 H, COCH₃), 2.11–2.07 (m, 1 H, H-2_a), 2.01, 1.79 (2 s, 6 H, 2 COCH₃). ESI-MS: m/z = 455.1 [M + Na]⁺. Anal. Calcd for C₂₂H₂₄O₇S (432.12): C, 61.10; H, 5.59. Found: C, 61.0; H, 5.77. p-Methoxyphenyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (20) ¹H NMR (200 MHz, CDCl₃): δ = 7.36–7.22 (m, 2 H, ArH), 6.79–6.75 (m, 2 H, ArH), 5.51–5.48 (m, 1 H, H-1), 5.29 (br s, 1 H, H-4), 5.24–5.14 (m, 1 H, H-3), 4.68–4.62 (m, 1 H, H-5), 4.07–4.00 (m, 2 H, H-6_ab), 3.73 (s, 3 H, OCH₃), 2.45–2.29 (m, 1 H, H-2_e), 2.07 (s, 3 H, COCH₃), 2.01–1.86 (m, 1 H, H-2_a), 1.96, 1.94 (2 s, 6 H, 2 COCH₃). ¹³C NMR (125 MHz, CDCl₃): δ = 170.3, 170.1, 169.8, 159.9, 134.9 (2 C), 124.0, 114.7 (2 C), 84.7, 67.4, 66.8 (2 C), 62.4, 55.3, 30.6, 20.9, 20.0 (2 C). ESI-MS: m/z = 435.1 [M + Na]⁺. Anal. Calcd for C₁₉H₂₄O₈S (412.12): C, 55.33; H, 5.87. Found: C, 55.20; H, 6.0. p-Bromophenyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (21) ¹H NMR (200 MHz, CDCl₃): δ = 7.44–7.31 (m, 4 H, ArH), 5.73–5.70 (m, 1 H, H-1), 5.35 (br s, 1 H, H-4), 5.28–5.19 (m, 1 H, H-3), 4.66–4.60 (m, 1 H, H-5), 4.10–4.06 (m, 2 H, H-6_ab), 2.56–2.40 (m, 1 H, H-2_e), 2.14 (s, 3 H, COCH₃), 2.13–2.07 (m, 1 H, H-2_a), 2.00, 1.99 (2 s, 6 H, 2 COCH₃). ¹³C NMR (125 MHz, CDCl₃): δ = 170.1, 169.9, 169.6, 133.0–121.7 (ArC), 83.4, 67.7, 66.5 (2 C), 62.2, 30.5, 20.7, 20.6 (2 C). ESI-MS: m/z = 483.0 [M + Na]⁺. Anal. Calcd for C₁₈H₂₁BrO₇S (460.02): C, 46.86; H, 4.59. Found: C, 46.70; H, 4.80. Benzenesulfonamido 2,3,6-Tri-deoxy-α-l-erythro-hex-2-enopyranoside (22) ¹H NMR (500 MHz, CDCl₃): δ = 7.87–7.40 (m, 5 H, ArH), 6.56 (d, J = 7.9 Hz, 1 H, NH), 5.79–5.76 (m, 1 H, H-2), 5.72–5.70 (m, 1 H, H-3), 5.48–5.46 (m, 1 H, H-1), 4.83–4.80 (m, 1 H, H-4), 3.33–3.29 (m, 1 H, H-5), 1.97 (s, 3 H, COCH₃), 0.57 (d, J = 6.0 Hz, 3 H, CCH₃). ¹³C NMR (125 MHz, CDCl₃): δ = 170.3, 141.8–126.7 (m, ArC, C-2, C-3), 76.8, 69.9, 64.9, 20.9, 17.1. ESI-MS: m/z = 334.0 [M + Na]⁺. Anal. Calcd for C₁₄H₁₇NO₅S (311.08): C, 54.01; H, 5.50. Found: C, 53.85; H, 5.69.