Acetic Anhydride → HCID 86584336, compound

HRID 1446030Notes

Reaction equation

HRID 1446030 reaction equation
[CH2:1]([O:8][CH2:9][C:10]([NH:12][C@H:13]1[C@@H:19]([OH:20])[C@H:18]([OH:21])[C@@H:17]([CH2:22][OH:23])[O:16][CH:14]1[OH:15])=[O:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(O[C:28](=[O:30])[CH3:29])(=O)C>N1C=CC=CC=1.CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:1]([O:15][CH:14]1[O:16][C@H:17]([CH2:22][O:23][C:28](=[O:30])[CH3:29])[C@@H:18]([O:21][C:14](=[O:15])[CH3:13])[C@H:19]([O:20][C:10](=[O:11])[CH3:9])[C@@H:13]1[NH:12][C:10](=[O:11])[CH2:9][O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)(=[O:8])[CH3:2]

Participants

6

Reactant 2

HCID 7918Acetic AnhydrideHCID 14160780N-Benzyloxyacetylmannosamine

Product 1

HCID 86584336HCID 86584336, compoundYield 192.8%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 31 (512 mg, 1.56 mmol) in pyridine (5 mL) was cooled to 0° C. To this solution was added acetic anhydride (2.5 mL, 27 mmol) and a catalytic amount of DMAP. The reaction mixture was stirred overnight and allowed to warm to rt. The resulting light yellow solution was diluted with CH2Cl2 (100 mL) and washed with 1 N HCl (3×50 mL), sat. NaHCO3 (2×50 mL), water (2×50 mL) and sat. NaCl (1×50 mL). The combined aqueous layers were back extracted with 50 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and concentrated. The crude product was purified by silica gel chromatography eluting with a gradient of 1:4 to 1:1 EtOAc/hexanes to afford 745 mg (96%) of a light yellow oil. IR (thin film): 3409, 2959, 2357, 1750, 1692, 1520 cm−1. 1H NMR (300 MHz, CDCl3): δ 1.90 (s, 6H), 1.99 (s, 6H), 2.06 (s, 6H), 2.18 (s, 6H), 3.79-3.84 (m, 1H), 3.91-3.99 (m, 1H), 4.02 (d, 2H, J=2.8), 4.04-4.07 (m, 2H), 4.14 (dd, 2H, J=2.7, 17.8), 4.20 (dd, 1H, J=3.9, 9.1), 4.55app t, 1H, J=6.3), 4.60-4.65 (m, 4H), 4.66-4.68 (m, 1H), 4.79 (ddd, 1H, J=1.6, 3.8, 13.2), 5.07 (dd, 1H, J=3.9, 9.8), 5.19 (app t, 1H, J=4.7), 5.24 (app t, 1H, J=9.8), 5.35 (dd, 1H, J=4.2, 10.2), 5.90 (d, 1H, J=1.6), 6.03 (d, 1H, J=1.6), 6.89 (d, 1H, J=9.6), 7.03 (d, 1H, J=9.3), 7.32-7.39 (m, 10H). 13C NMR (125 MHz, CDCl3): δ 20.3, 20.4, 20.6, 20.7, 20.8, 48.6, 61.7, 65.1, 65.2, 68.9, 69.1, 69.3, 70.2, 71.3, 73.3, 73.5, 73.6, 77.8, 97.1, 127.8, 127.9, 128.2, 128.3, 128.4, 128.6, 128.7, 136.4, 136.6, 169.4, 169.7, 170.1, 170.5. MS (FAB) m/z 496 (MH+). Anal. Calcd for C23H29NO11: C, 55.75; H, 5.90; N, 2.83; Found: C, 55.54; H, 5.93; N, 2.68.

Workup

  1. washwashed with 1 N HCl (3×50 mL), sat. NaHCO3 (2×50 mL), water (2×50 mL) and sat. NaCl (1×50 mL)
  2. extractionThe combined aqueous layers were back extracted with 50 mL of CH2Cl2
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. concentrationconcentrated
  5. customThe crude product was purified by silica gel chromatography
  6. washeluting with a gradient of 1:4 to 1:1 EtOAc/hexanes

Sources & evidence

ORD record
ord-fb060c3e3860470c92270533dea7882f
Source dataset
uspto-grants-2010_02
Patent number
US07667012B2

Reaction notes

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