tert-Butyldimethylsilyl trifluoromethanesulphonate → HCID 89784960, compound

HRID 1055919Notes

Reaction equation

HRID 1055919 reaction equation
[C:1]([C:4]1[CH:5]=[CH:6][CH:7]=[C:8]2[C:13]=1[N:12]=[C:11]([C:14]([O:16][CH3:17])=[O:15])[CH:10]=[CH:9]2)(=[O:3])[CH3:2].[Si:18](OS(C(F)(F)F)(=O)=O)([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19]>C(Cl)Cl>[Si:18]([O:3][C:1]([C:4]1[CH:5]=[CH:6][CH:7]=[C:8]2[C:13]=1[N:12]=[C:11]([C:14]([O:16][CH3:17])=[O:15])[CH:10]=[CH:9]2)=[CH2:2])([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19]

Participants

4

Reactant 2

HCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 89781946HCID 89781946, compound

Product 1

HCID 89784960HCID 89784960, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of methyl 8-acetylquinoline-2-carboxylate (1.98 g, 8.64 mmol) in DCM (25 mL) at 0° C. was added TEA (1.56 mL, 11.23 mmol) followed by TBSOTf (1.66 mL, 9.50 mmol). The reaction mixture was stirred at 0° C. for 50 min. The mixture was then partitioned between saturated NaHCO3 and DCM. The organic layer was separated, and the aq. layer was extracted with DCM (2×). The combined organic layers were then dried over anhydrous MgSO4, filtered, and concentrated in vacuo to give methyl 8-(1-((tert-butyldimethylsilyl)oxy)vinyl)quinoline-2-carboxylate as a brown oil: 1H NMR (400 MHz, CDCl3) δ ppm 8.29 (d, J=8.4 Hz, 1H), 8.18 (d, J=8.4 Hz, 1H), 8.12 (dd, J=7.3, 1.3 Hz, 1H), 7.80 (dd, J=8.1, 1.3 Hz, 1H), 7.62 (t, J=7.7 Hz, 1H), 6.12 (s, 1H), 4.99 (s, 1H), 4.05 (s, 3H), 1.01 (s, 9H), 0.28 (s, 6H). m/z (ESI, +ve ion) 344.0 (M+H)+. This oil was taken up in THF (10 mL), treated with water (2.5 mL, 138 mmol) and NBS (1.61 g, 9.07 mmol), and stirred at RT for 20 min. The reaction mixture was then partitioned between water and Et2O, and the organic layer was separated and sequentially washed with saturated NaHCO3, water, and brine, then dried over MgSO4, filtered, and concentrated in vacuo to give methyl 8-(2-bromoacetyl)quinoline-2-carboxylate as a greenish-brown solid. This material was used without purification in the subsequent step assuming the theoretical yield: 1H NMR (400 MHz, CDCl3) δ ppm 8.40 (d, J=8.6 Hz, 1H), 8.30 (d, J=7.0 Hz, 1H), 8.26 (d, J=8.6 Hz, 1H), 8.09 (d, J=8.2 Hz, 1H), 7.76 (t, J=7.6 Hz, 1H), 5.32 (br. s., 2H), 4.08 (s, 3H). m/z (ESI, +ve ion) 308.0/310.1 (M+H)+.

Workup

  1. customThe mixture was then partitioned between saturated NaHCO3 and DCM
  2. customThe organic layer was separated
  3. extractionthe aq. layer was extracted with DCM (2×)
  4. dry with materialThe combined organic layers were then dried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f6842810fae64af28dc3538ebed05a27
Source dataset
uspto-grants-2016_07
Patent number
US09394297B2

Reaction notes

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