Sodium Carbonate → tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-hydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate

HRID 75742Notes

Reaction equation

HRID 75742 reaction equation
[CH2:1]([C@@H:8]1[C@@H:16]([O:17][Si](C(C)(C)C)(C)C)[C@H:15]([CH3:25])[O:14][C:13](=[O:26])[C@@H:12]([NH:27][C:28](=[O:34])[O:29][C:30]([CH3:33])([CH3:32])[CH3:31])[CH2:11][O:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CC=CC=1.C1COCC1.C1C=CN=CC=1.F.C([O-])([O-])=O.[Na+].[Na+]>CCOC(C)=O>[C:30]([O:29][C:28](=[O:34])[NH:27][C@H:12]1[CH2:11][O:10][CH2:9][C@H:8]([CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C@@H:16]([OH:17])[C@H:15]([CH3:25])[O:14][C:13]1=[O:26])([CH3:32])([CH3:31])[CH3:33]

Participants

6

Reactant 4

HCID 10340Sodium Carbonate2×HCID 64774Pyridine, hydrofluoride (1:1)HCID 16069498Pyridine tetrahydrofuranHCID 89890039tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-((tert-butyldimethylsilyl)oxy)-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate

Product 1

HCID 86701245tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-hydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamateYield 90%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A solution of tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-((tert-butyldimethylsilyl)oxy)-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate (120 mg, 0.24 mmol) in a solution of HF/pyridine/THF (5:3:8 ratio, 1.2 mL) was stirred at room temperature. After 16 h, an additional 0.1 mL HF-pyridine solution was added and the reaction was allowed to stir for 2 h. The crude reaction was diluted with EtOAc (5 mL) and added to sat'd aq Na2CO3 (5 mL) dropwise. Additional sat'd aq Na2CO3 was added until bubbling was no longer observed. The EtOAc layer was separated and the aqueous phase was extracted with EtOAc (2×). The combined organic layers were dried over Na2SO4, filtered, and concentrated to furnish tert-butyl-(3S,7S,8R,9S)-7-benzyl-8-hydroxy-9-methyl-2-oxo-1,5-dioxonan-3-ylcarbamate as a colorless oil (82 mg, 89%): 1H NMR (400 MHz, CDCl3) δ 7.32-7.26 (m, 3H), 7.20 (dd, J=8.2, 6.4 Hz, 2H), 5.15 (d, J=8.5 Hz, 1H), 4.88 (m, 1H), 4.65 (d, J=7.6 Hz, 1H), 3.90 (dd, J=11.7, 7.5 Hz, 1H), 3.57 (d, J=10.3 Hz, 1H), 3.44 (m, 2H), 3.33 (m, 1H), 3.11 (dd, J=13.8, 4.3 Hz, 1H), 2.49 (m, 1H), 1.87 (s, 1H), 1.48 (d, J=6.4 Hz, 3H), 1.43 (d, J=4.3 Hz, 9H); ESIMS m/z 378.4 ([M−H]).

Workup

  1. customThe crude reaction
  2. additionwas added
  3. customuntil bubbling
  4. customThe EtOAc layer was separated
  5. extractionthe aqueous phase was extracted with EtOAc (2×)
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-060f425d52bf44f89161cc019a5c5a3c
Source dataset
uspto-grants-2014_09
Patent number
US08835462B2

Reaction notes

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