Isobutyryl chloride → HCID 89892585, compound

HRID 2283017Notes

Reaction equation

HRID 2283017 reaction equation
[OH:1][C@@H:2]1[C@@H:10]([OH:11])[C@H:9]([CH3:12])[O:8][C:7](=[O:13])[C@@H:6]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[CH2:5][O:4][CH2:3]1.[C:22](Cl)(=[O:26])[CH:23]([CH3:25])[CH3:24]>N1C=CC=CC=1.CN(C1C=CN=CC=1)C>[CH3:24][CH:23]([CH3:25])[C:22]([O:1][C@@H:2]1[C@@H:10]([O:11][C:22](=[O:26])[CH:23]([CH3:25])[CH3:24])[C@H:9]([CH3:12])[O:8][C:7](=[O:13])[C@@H:6]([NH:14][C:15]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:21])[CH2:5][O:4][CH2:3]1)=[O:26]

Participants

5

Reactant 2

HCID 62325Isobutyryl chlorideHCID 89892584HCID 89892584, compound

Product 1

HCID 89892585HCID 89892585, compound

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Procedure

To a solution of tert-butyl ((3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate (115.0 mg, 0.245 mmol) in pyridine (1.75 mL) was added DMAP (6.40 mg, 0.0520 mmol) followed by isobutyryl chloride (0.10 mL, 0.956 mmol) at 0° C. and the reaction was slowly warmed to room temperature and stirred for 16 h. The reaction mixture was quenched with H2O and the reaction was stirred at room temperature for 30 min and then extracted with Et2O. The phases were separated and the aqueous phase was further extracted with Et2O. The combined organic phases were washed with brine, 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, thick oil (115 mg, 94%): IR (neat) 3353, 2976, 1742, 1519, 1368, 1251, 1155 cm−1; 1H NMR (400 MHz, CDCl3) δ 5.41 (d, J=8.2 Hz, 1H), 5.21-5.12 (m, 1H), 5.12-5.04 (m, 1H), 4.92-4.83 (m, 1H), 4.74 (dd, J=13.4, 6.9 Hz, 1H), 3.95 (dd, J=11.7, 7.0 Hz, 1H), 3.80-3.65 (m, 3H), 2.64-2.41 (m, 2H), 1.44 (s, 9H), 1.32 (d, J=6.2 Hz, 3H), 1.20 (d, J=7.0 Hz, 3H), 1.16 (d, J=7.0 Hz, 3H), 1.14 (d, J=7.0 Hz, 3H), 1.10 (d, J=7.0 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 175.57, 175.47, 171.37, 155.18, 80.34, 74.52, 74.30, 74.15, 73.35, 71.34, 34.01, 33.91, 28.30, 19.01, 18.88, 18.74, 18.71, 18.03; HRMS-ESI (m/z) [M]+ calcd for C21H35NO9, 445.2312; found, 445.2322.

Workup

  1. customThe reaction mixture was quenched with H2O
  2. stirringthe reaction was stirred at room temperature for 30 min
  3. extractionextracted with Et2O
  4. customThe phases were separated
  5. extractionthe aqueous phase was further extracted with Et2O
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated
  10. custompurified by flash chromatography (SiO2, hexanes/EtOAc gradient)

Sources & evidence

ORD record
ord-564b849bf0d94019a4bfee1f8e7b61f9
Source dataset
uspto-grants-2015_09
Patent number
US09144239B2

Reaction notes

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