Peracetic Acid → HCID 60168011, compound

HRID 60397Notes

Reaction equation

HRID 60397 reaction equation
Br[C:2]1[C:3]([CH3:22])=[C:4]2[CH2:20][CH2:19][N:18]([CH3:21])[C:5]2=[N:6][C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17].CN(C)CCN(C)C.[Li]CCCC.COB(OC)OC.[C:43]([O:46]O)(=[O:45])[CH3:44].C(N(CC)CC)C.C(OC(=O)C)(=O)C>C1COCC1.CN(C1C=CN=CC=1)C.O>[C:43]([O:46][C:2]1[C:3]([CH3:22])=[C:4]2[CH2:20][CH2:19][N:18]([CH3:21])[C:5]2=[N:6][C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])(=[O:45])[CH3:44]

Participants

11

Reactant 7

HCID 6585Peracetic AcidHCID 7918Acetic AnhydrideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8470Trimethyl borateHCID 8471TriethylamineHCID 716778985-Bromo-1,4-dimethyl-6-decyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridineHCID 178418339Butyllithium

Product 1

HCID 60168011HCID 60168011, compound

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 43.0 mg (0.12 mmol) of 5-bromo-1,4-dimethyl-6-decyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine in 1 mL of THF was added 17.4 μL (0.12 mmol) of tetramethylethylenediamine (TMEDA) at −78° C. followed by 146.3 μL (0.23 mmol, 1.6 M in hexanes) of n-BuLi. After 30 min, 28.7 μL (0.26 mmol) of trimethoxy boron was added and the resulting mixture was stirred for another 1 h. To the reaction mixture was added slowly 54.2 μL (0.26 mmol, 32 wt %) of peracetic acid and the solution was then warmed to 0° C. over a period of 30 min. The mixture was diluted by 5 mL of H2O and extracted with three 5-mL portions of EtOAc. The combined organic layer was washed with brine, dried (MgSO4) and the solvent was concentrated under diminished pressure. The resulting oil was dissolved in 2 mL of CH2Cl2 at 0° C., followed by the addition of 97.9 μL (0.70 mmol) of triethylamine, 1.4 mg (0.01 mmol) of DMAP and 33.1 μL (0.35 mmol) of acetic anhydride. The reaction was stirred at room temperature for 1 h and quenched by the addition of 2 mL of sat aq NH4Cl. The solution was then extracted with three 5-mL portions of EtOAc. The combined organic layer was washed with brine, dried (MgSO4) and the solvent was concentrated under diminished pressure. The residue was purified by flash chromatography on a silica gel column (20 1.7 cm). Elution with 100:1 hexanes/ethyl acetate gave 2b as a yellow oil: yield 28.0 mg (68%); silica gel TLC Rf 0.15 (3:7 EtOAt/hexanes); 1H NMR (CDCl3) δ 0.86 (t, 3H, J=6.8 Hz), 1.24-1.28 (m, 16H), 1.60 (quint, 2H, J=7.6 Hz), 1.92 (s, 3H), 2.28 (s, 3H), 2.44 (t, 2H, J=8.0 Hz), 2.82 (t, 2H, J=8.4 Hz), 2.87 (s, 3H) and 3.41 (t, 2H, J=8.4 Hz); 13C NMR (CDCl3) δ 12.9, 14.1, 20.5, 22.7, 24.6, 28.7, 29.3, 29.5, 29.6, 28.6, 31.9, 32.5, 33.3, 52.8, 120.1, 134.7, 136.5, 149.7, 161.2 and 169.9; mass spectrum, m/z 346.3 (M)+ (theoretical 246.3); mass spectrum (APCI), m/z 347.2696 (M+H)+ (C21H35N2O2 requires 347.2699).

Workup

  1. extractionextracted with three 5-mL portions of EtOAc
  2. washThe combined organic layer was washed with brine
  3. dry with materialdried (MgSO4)
  4. concentrationthe solvent was concentrated under diminished pressure
  5. dissolutionThe resulting oil was dissolved in 2 mL of CH2Cl2 at 0° C.
  6. stirringThe reaction was stirred at room temperature for 1 h
  7. customquenched by the addition of 2 mL of sat aq NH4Cl
  8. extractionThe solution was then extracted with three 5-mL portions of EtOAc
  9. washThe combined organic layer was washed with brine
  10. dry with materialdried (MgSO4)
  11. concentrationthe solvent was concentrated under diminished pressure
  12. customThe residue was purified by flash chromatography on a silica gel column (20 1.7 cm)
  13. washElution with 100:1 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-a7263f09b06a4f99a577808daf2de1c0
Source dataset
uspto-grants-2016_09
Patent number
US09440967B2

Reaction notes

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