Pyridine → HCID 88236211, compound

HRID 1637419Notes

Reaction equation

HRID 1637419 reaction equation
FC(F)(F)S([O:6][S:7]([C:10]([F:13])([F:12])[F:11])(=[O:9])=[O:8])(=O)=O.[CH3:16][O:17][C:18]1[CH:41]=[CH:40][C:21]([CH2:22][O:23][C@H:24]2[C@@H:36]([OH:37])[C@@H:35](O)[C@H:34]([CH3:39])[O:33][C@@H:25]2[S:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[CH:20][CH:19]=1.N1C=CC=CC=1>C(Cl)Cl>[F:11][C:10]([F:13])([F:12])[S:7]([O:37][C@H:36]1[C@@H:35]([O:6][S:7]([C:10]([F:11])([F:12])[F:13])(=[O:8])=[O:9])[C@H:34]([CH3:39])[O:33][C@H:25]([S:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@H:24]1[O:23][CH2:22][C:21]1[CH:40]=[CH:41][C:18]([O:17][CH3:16])=[CH:19][CH:20]=1)(=[O:8])=[O:6]

Participants

5

Reactant 3

HCID 1049PyridineHCID 67749Trifluoromethanesulfonic anhydrideHCID 53958828HCID 53958828, compound

Product 1

HCID 88236211HCID 88236211, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Trifluoromethanesulfonic anhydride (1.8 mL, 10.8 mmol) is added at 0° C. to a solution of phenyl 6-deoxy-2-O-(4-methoxybenzyl)-1-thio-β-L-allopyranoside (β-14) (1.01 g, 2.69 mmol) and pyridine (2.2 mL, 26.9 mmol) in 30 mL of CH2Cl2. The solution is stirred at 0° C. for 1 h and allowed to warm at room temperature over 3 h. The reaction mixture is cooled to 0° C. before quenching with TEA (1.0 mL, 7.2 mmol). The reaction mixture is diluted with 30 mL of CH2Cl2, washed with saturated NaHCO3 (30 mL), 1N HCl (30 mL), dried over Na2SO4, filtered and concentrated. The crude product is purified by flash chromatography (8% EtOAc/petroleum ether) to give 1.36 g (79%) of phenyl 6-deoxy-3,4-di-O-(trifluoromethanesulfonyl)-2-O-(4-methoxybenzyl)-1-thio-β-L-allopyranoside (β-15): Rf 0.49 (20% EtOAc/petroleum ether); 1H NMR (CDCl3, 270 MHz) δ 7.48 (d, 2H, ArH), 7.33-7.21 (m, SH, ArH), 6.91 (d, 2H, ArH), 5.34 (t, J=2.0 Hz, 1H, H-3), 4.93 (d, J=9.2 Hz, 1H, H-1), 4.77 (d, J=11.2 Hz, 1H, CH2), 4.65 (d, J=11.2 Hz, 1H, CH2), 4.55 (dd, J=2.0, 8.8 Hz, 1H, H-4), 4.19-3.96 (m, 1H, H-5), 3.90 (s, 3H, OCH3), 3.47 (dd, J=2.0, 9.2 Hz, 1H, H-2), 1.36 (d, J=5.8 Hz, 3H, H-6).

Workup

  1. temperatureto warm at room temperature over 3 h
  2. temperatureThe reaction mixture is cooled to 0° C.
  3. washwashed with saturated NaHCO3 (30 mL), 1N HCl (30 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product is purified by flash chromatography (8% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-94164d4714a54394b5ff776c23d2a257
Source dataset
uspto-grants-2000_03
Patent number
US06040433

Reaction notes

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