Tetrabutylammonium Fluoride → HCID 71152401, compound

HRID 1497279Notes

Reaction equation

HRID 1497279 reaction equation
CS(O[CH2:6][C@@H:7]1[C@@H:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@H:15]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@H:10]2[NH:11][C:12](=[O:14])[O:13][C@H:9]2[CH2:8]1)(=O)=O.[F-:33].C([N+](CCCC)(CCCC)CCCC)CCC>C(#N)C>[CH2:26]([O:25][C@@H:15]1[C@H:10]2[NH:11][C:12](=[O:14])[O:13][C@H:9]2[CH2:8][C@H:7]([CH2:6][F:33])[C@H:16]1[O:17][CH2:18][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 89315659HCID 89315659, compound

Product 1

HCID 71152401HCID 71152401, compoundYield 43.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

To a solution of ((3aS,4R,5R,6R,7aS)-4,5-bis(benzyloxy)-2-oxooctahydrobenzo[d]oxazol-6-yl)methyl methanesulfonate (2.24 g, 4.86 mmol) in dry acetonitrile (12 mL) at room temperature was added a solution of tetrabutylammonium fluoride (4.933 g, 24.3 mmol) in dry acetonitrile (16 mL). The mixture was heated at reflux under N2 for 4 h. Solvent was evaporated under reduced pressure. The residue was dissolved in EtOAc (150 mL), washed with water (2×) and brine, and dried with MgSO4. The solvent was evaporated to give the crude product. This was purified by SiO2 column, eluted with 30-50% EtOAc in hexanes to give (3aS,4R,5R,6S,7aS)-4,5-bis(benzyloxy)-6-(fluoromethyl)hexahydrobenzo[d]oxazol-2(3H)-one (810 mg, 43%). MS m/z 408.1 (M+23, 100%); 1H NMR (400 MHz, CDCl3) δ 7.31-7.42 (m, 10H), 4.99 (s, 1H), 4.93 (d, J=11.7 Hz, 1H), 4.84 (d, J=11.0 Hz, 1H), 4.79 (dd, J=9.2 Hz, 3.2 Hz, 0.5H), 4.65-4.71 (m, 1.5H), 4.65 (d, J=11.1 Hz, 1H), 4.59 (d, J=11.7 Hz, 1H), 4.37 (ddd, J=47.4 Hz, 9.2 Hz, 2.3 Hz, 1H), 3.58 (t, J=6.8 Hz, 1H), 3.51 (t, J=7.8 Hz, 1H), 3.44 (t, J=8.9 Hz, 1H), 2.22 (dt, J=14.9 Hz, 2.9 Hz, 1H), 1.94-2.10 (m, 1H), 1.85-1.93 (m, 1H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux under N2 for 4 h
  3. customSolvent was evaporated under reduced pressure
  4. dissolutionThe residue was dissolved in EtOAc (150 mL)
  5. washwashed with water (2×) and brine
  6. dry with materialdried with MgSO4
  7. customThe solvent was evaporated
  8. customto give the crude product
  9. customThis was purified by SiO2 column
  10. washeluted with 30-50% EtOAc in hexanes

Sources & evidence

ORD record
ord-73d9e41286254ab5a33c76090a15e55f
Source dataset
uspto-grants-2015_12
Patent number
US09199949B2

Reaction notes

Loading…