Ethyl Acetate → HCID 86701324, compound

HRID 2283018Notes

Reaction equation

HRID 2283018 reaction equation
[C:1]([O:5][C:6]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H](O)[C@@H:20](O)[C@H:19]([CH3:27])[O:18][C:17]1=[O:28])[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:7])([CH3:4])([CH3:3])[CH3:2].[O-]S([O-])(=O)=O.[Na+].[Na+].CN(C1C2C(N(C)C)=CC=CC=2C=CC=1)C.F[B-](F)(F)F.C[O+:58]([CH3:60])[CH3:59].C[CH2:62][O:63]C(C)=O>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H:59]([O:58][CH3:60])[C@@H:20]([O:63][CH3:62])[C@H:19]([CH3:27])[O:18][C:17]1=[O:28])[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:12])[CH3:13])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 5

HCID 8857Ethyl AcetateHCID 24436Sodium SulfateHCID 88675Proton spongeHCID 2735153Oxonium, trimethyl-, tetrafluoroborate(1-) (1:1)HCID 86701319HCID 86701319, compound

Product 1

HCID 86701324HCID 86701324, compoundYield 57%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl]carbamate (0.220 g, 0.543 mmol) and Na2SO4 (500 mg) in CH2Cl2 (5.4 mL) at 0° C. was added Proton-Sponge™ (1.63 g, 7.60 mmol) and trimethyloxonium tetrafluoroborate (0.562 g, 3.80 mmol). The reaction mixture was slowly warmed to room temperature and stirred overnight. The reaction mixture was diluted with EtOAc and filtered. The organic layer was washed successively with H2O, 1 M aqueous NaHSO4, and saturated aqueous NaHCO3. The organic layer was dried over MgSO4, filtered, and the filtrate was concentrated and purified by flash chromatography (SiO2, hexanes/EtOAc gradient) to yield the title compound as a colorless oil (133 mg, 57%): IR (neat) 2980, 2935, 1746, 1707, 1367, 1254, 1106 cm−1; 1H NMR (400 MHz, CDCl3) δ 5.19 (dd, J=8.9, 4.2 Hz, 1H), 4.75 (dq, J=9.4, 6.3 Hz, 1H), 4.23 (dd, J=12.1, 4.2 Hz, 1H), 3.89 (dd, J=12.1, 9.0 Hz, 1H), 3.80 (d, J=10.6 Hz, 1H), 3.56-3.48 (m, 1H), 3.52 (s, 3H), 3.42 (s, 3H), 3.17-3.11 (m, 1H), 3.06 (t, J=9.0 Hz, 1H), 1.48 (s, 18H), 1.40 (d, J=6.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 169.10, 152.73, 86.77, 85.12, 83.13, 75.07, 72.76, 72.52, 61.21, 58.43, 57.94, 28.03, 18.65; HRMS-ESI (m/z) [M]+ calcd for C20H35NO9, 433.2312; found, 433.2317.

Workup

  1. filtrationfiltered
  2. washThe organic layer was washed successively with H2O, 1 M aqueous NaHSO4, and saturated aqueous NaHCO3
  3. dry with materialThe organic layer was dried over MgSO4
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated
  6. custompurified by flash chromatography (SiO2, hexanes/EtOAc gradient)

Sources & evidence

ORD record
ord-1136b640508f4b8c939a4dc87742601e
Source dataset
uspto-grants-2015_09
Patent number
US09144239B2

Reaction notes

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