Zn(II) Triflate-Catalyzed N-Glycosylation
141
literature data; characterization data of new products are outlined in the ex-
perimental section.
4,6-Di-O-acetyl-2,3-dideoxy-α/β-D-erythro-hex-2-enopyranosyl-N-methylglyci-
nate-p-toluenesulfonamide (3m)
Yield: 107 mg (64%). Rf (40% EtOAc/Hexane) 0.6. IR (CHCl3, cm−1): 3022,
1
2926, 2855, 1736, 1371, 1236, 1044, 752, 667. H NMR (300 MHz, CDCl3): δ
7.83 and 7.28 (each d, J = 8.3 Hz, 2H each, Ph), 6.08 (d, J = 2.5 Hz, 1H, H-1),
5.99–5.90 (m, 3H, H-3 both isomers, H-2), 5.83 (dt, J = 10.2, 2.3 Hz, 1H, H-2),
5.44 (br s, 1H, H-1), 5.33 (dd, J = 9.6, 1.5 Hz, 1H, H-4), 5.17 (dd, J = 9.1, 2.5 Hz,
1H, H-4), 4.22–4.07 (6H, CH2COOCH3, H-6a both isomers), 3.99 (dd, J = 12.1,
6.0 Hz, 1H, H-6b), 3.87 (m, 1H, H-5), 3.77 (dd, J = 9.5, 5.5 Hz, 1H, H-6b),
3.73–3.62 (m, 7H, OCH3 both isomers, H-5), 2.43 (s, 6H, CH3Ph), 2.10–2.07
(s, 12H, CH3COO). 13C NMR (75 MHz, CDCl3): δ 170.7, 170.5, 170.2, 169.5,
143.9, 135.8, 131.4, 129.6, 129.3, 128.5, 128.2, 127.3, 90.5, 82.7, 74.0, 67.3, 65.2,
64.2, 62.9, 52.4, 43.8, 31.8, 21.5, 20.9, 20.7. MS (ESI) m/z: 473 ([M+NH4]+, 70),
478 ([M+Na]+, 100). HRMS (ESI): m/z [M+Na]+ calcd. for C20H25NO9SNa+:
478.11422; found: 478.11165.
4,6-Di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl-benzenesulfonamide
(3u)
Yield: 97.7 mg (72%). Rf (40% EtOAc/Hexane) 0.5. IR (CHCl3, cm−1): 3020,
1
1742, 1371, 1214, 742, 667. H NMR (500 MHz, CDCl3): 7.94 (d, J = 8.09 Hz,
2H, Ph), 7.60 (t, J = 7.6 Hz, 1H, Ph), 7.53 (t, J = 7.5 Hz, 2H, Ph), 6.16–6.13 (m,
2H, H-3, NH), 5.99 (dd, J = 9.9, 3.2 Hz, 1H, H-2), 5.65 (m, 1H, H-1), 4.94 (m,
1H, H-4), 3.94–3.88 (m, 2H, H-6a, H-5), 3.35 (dd, J = 8.9, 3.4 Hz, 1H, H-6b),
2.03 (s, 3H, CH3COO), 1.95 (s, 3H, CH3COO). 13C NMR (125 MHz, CDCl3): δ
170.4, 170.2, 141.4, 132.8, 129.3, 129.0, 127.0, 126.5, 76.7, 66.4, 61.5, 61.2, 20.7,
20.6. MS (ESI) m/z: 387 ([M+NH4]+, 100), 392 ([M+Na]+, 50).HRMS (ESI): m/z
[M+Na]+ calcd. for C16H19NO7SNa+: 392.07744; found: 392.07679.
4,6-Di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl-4’-tert-butylphenyl-
sulfonamide (3w)
Yield: 121.9 mg (78%). Rf (40% EtOAc/Hexane) 0.4. IR (CHCl3, cm−1): 3021,
2963, 2924, 1741, 1369, 1216, 1021, 750, 669, 630. 1H NMR (300 MHz, CDCl3):
δ 7.86 (d, J = 8.7 Hz, 2H, Ph), 7.54 (d, J = 8.7 Hz, 2H, Ph), 6.13 (dd, J =
5.7, 1.5 Hz, 1H, H-3), 6.00 (dd, J = 9.8, 3.0 Hz, 1H, H-2), 5.88 (d, J = 9.1 Hz,
1H, NH), 5.64 (m, 1H, H-1), 4.95 (dd, J = 5.3, 1.9 Hz, 1H, H-4), 3.96–3.70 (m,
2H, H-6a, H-5), 3.25 (dd, J = 9.8, 4.5 Hz, 1H, H-6b), 2.03 (s, 3H, CH3COO),
1.95 (s, 3H, CH3COO), 1.34 (s, 9H, C(CH3)3). 13C NMR (125 MHz, CDCl3): δ
170.2, 170.1, 156.6, 138.5, 129.3, 126.9, 126.8, 126.4, 126.0, 76.6, 66.1, 61.4,
60.9, 35.1, 30.9, 20.6, 20.5. MS (ESI) m/z: 443 ([M+NH4]+, 100), 448 ([M+Na]+,