(Bis(2-methoxyethyl)amino)sulfur trifluoride → HCID 71153377, compound

HRID 1497298Notes

Reaction equation

HRID 1497298 reaction equation
O[C@@H:2]1[C@H:7]2[N:8]([CH:12]([O:19][CH3:20])[C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:9](=[O:11])[O:10][C@H:6]2[CH2:5][C@@H:4]2[CH2:21][O:22][CH:23]([C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[O:24][C@@H:3]12.COCCN(S(F)(F)[F:41])CCOC>C(Cl)Cl.C([O-])(O)=O.[Na+]>[F:41][C@H:2]1[C@H:7]2[N:8]([CH:12]([O:19][CH3:20])[C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=3)[C:9](=[O:11])[O:10][C@H:6]2[CH2:5][C@@H:4]2[CH2:21][O:22][CH:23]([C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[O:24][C@@H:3]12

Participants

5

Reactant 2

HCID 2734690(Bis(2-methoxyethyl)amino)sulfur trifluorideHCID 71153404HCID 71153404, compound

Product 1

HCID 71153377HCID 71153377, compoundYield 51%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a solution of (3aR,4R,4aR,8aR,9aS)-4-hydroxy-3-(methoxy(phenyl)methyl)-6-phenyloctahydro-2H-[1,3]dioxino[5′,4′:4,5]benzo[1,2-d]oxazol-2-one (1.77 g, 4.31 mmol) in dry DCM (25 mL) at room temperature was added bis(2-methoxyethyl)aminosulfur trifluoride (3.81 g, 17.2 mmol). The mixture was stirred at room temperature under N2 for 20 h. The mixture was slowly diluted with saturated aqueous NaHCO3 (80 mL), extracted with EtOAc (2×50 mL). The extracts were washed with brine and dried with MgSO4. The solvents were evaporated to give the crude product. This was purified by SiO2 column, eluted with 25-35% EtOAc in hexanes to give (3aS,4S,4aR,8aR,9aS)-4-fluoro-3-(methoxy(phenyl)methyl)-6-phenyloctahydro-2H-[1,3]dioxino[5′,4′:4,5]benzo[1,2-d]oxazol-2-one (900 mg, 51%). MS m/z 436.6 (M+23, 100%); 1H NMR (400 MHz, CDCl3) δ 7.34-7.50 (m, 10H), 6.15 (s, 1H), 5.49 (s, 1H), 4.91 (dd, J=51.4 Hz, 3.0 Hz, 1H), 4.40 (d, J=5.0 Hz, 1H), 4.29 (dd, J=11.2 Hz, 4.8 Hz, 1H), 3.66 (s, 3H), 3.25-3.55 (m, 3H), 2.59-2.71 (m, 1H), 2.20-2.25 (m, 1H), 1.23-1.32 (m, 1H).

Workup

  1. extractionextracted with EtOAc (2×50 mL)
  2. washThe extracts were washed with brine
  3. dry with materialdried with MgSO4
  4. customThe solvents were evaporated
  5. customto give the crude product
  6. customThis was purified by SiO2 column
  7. washeluted with 25-35% EtOAc in hexanes

Sources & evidence

ORD record
ord-0f03baa2cf8c4b468b822e2e82bbdfeb
Source dataset
uspto-grants-2015_12
Patent number
US09199949B2

Reaction notes

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