tert-Butyldimethylsilyl trifluoromethanesulphonate → HCID 90272385, compound

HRID 925205Notes

Reaction equation

HRID 925205 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:21][CH2:20][C:10]2[C:11]3[C:12](=[O:19])[CH:13]([F:18])[CH2:14][C:15]=3[CH:16]=[CH:17][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2].[Si](OS(C(F)(F)[F:34])(=O)=O)(C(C)(C)C)(C)C.[B-](F)(F)(F)F.[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1>C(Cl)Cl.C(#N)C>[CH2:1]([O:3][C:4]([N:6]1[CH2:21][CH2:20][C:10]2[C:11]3[C:12](=[O:19])[C:13]([F:34])([F:18])[CH2:14][C:15]=3[CH:16]=[CH:17][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 2724933SelectfluorHCID 90237784HCID 90237784, compound

Product 1

HCID 90272385HCID 90272385, compound

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Into a 500 ml flask, the product from step (a) (6.01 g, 20.65 mmol) dissolved in DCM (100 ml) was added. The solution was cooled to 0° C. and TEA (17.27 ml, 123.91 mmol) was added, followed by TBDMS-triflate (14.222 ml, 61.95 mmol). After 10 minutes, the ice bath was removed and the mixture was stirred at room temperature for 16 hours. The contents were washed with saturated aqueous NaHCO3, 1M citric acid, saturated aqueous NaHCO3, brine, and dried over Na2SO4. Evaporation of solvent yielded a brown liquid which was immediately dissolved in acetonitrile (100 ml). The solution was cooled to 0° C. and Selectfluor (14.6 g, 41.3 mmol) was added portion-wise at 0° C. over 30 minutes. The flask was then warmed to room temperature and stirred for 1 hour. The contents were partitioned between DCM and water and the aqueous layer was extracted with DCM (3×). The combined DCM extracts were washed with brine, dried over Na2SO4, and solvent evaporated in vacuo to give the crude product. Purification by silica-gel chromatography (gradient elution: 0 to 40% EtOAc) gave the sub-title product an off-white solid (5.1 g). 1H NMR (300 MHz, CDCl3) δ7.45 (d, J=7.8 Hz, 1H); 7.23 (d, J=7.5 Hz, 1H); 4.16 (t, J=6.9 Hz, 2H); 3.63-3.57 (m, 6H); 3.46 (t, J=12.9 Hz, 2H); 3.01-2.98 (m, 2H); 1.27 (t, J=7.2 Hz, 3H); MS: ESI (positive): 310 (M+1).

Workup

  1. additionwas added
  2. customthe ice bath was removed
  3. washThe contents were washed with saturated aqueous NaHCO3, 1M citric acid, saturated aqueous NaHCO3, brine
  4. dry with materialdried over Na2SO4
  5. customEvaporation of solvent
  6. customyielded a brown liquid which
  7. temperatureThe solution was cooled to 0° C.
  8. temperatureThe flask was then warmed to room temperature
  9. stirringstirred for 1 hour
  10. customThe contents were partitioned between DCM and water
  11. extractionthe aqueous layer was extracted with DCM (3×)
  12. washThe combined DCM extracts were washed with brine
  13. dry with materialdried over Na2SO4, and solvent
  14. customevaporated in vacuo
  15. customto give the crude product
  16. customPurification
  17. washby silica-gel chromatography (gradient elution: 0 to 40% EtOAc)

Sources & evidence

ORD record
ord-38b219559cec4b369f35eed16870cd8b
Source dataset
uspto-grants-2016_03
Patent number
US09284277B2

Reaction notes

Loading…