N-bromobutanimide → HCID 69085611, compound

HRID 1396291Notes

Reaction equation

HRID 1396291 reaction equation
[C:1]([O:5][C:6](=[O:49])[N:7]([CH2:39][CH2:40][O:41][CH2:42][C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)[C:8]1[S:9][C@H:10]2[O:16][C@H:15]([CH2:17][OH:18])[C@@H:14]([O:19][CH2:20][C:21]3[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=3)[C@H:13]([O:29][CH2:30][C:31]3[CH:36]=[CH:35][C:34]([O:37][CH3:38])=[CH:33][CH:32]=3)[C@H:11]2[N:12]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:50]C1(C)N([O])C(C)(C)CCC1.C1C(=O)N(Br)C(=O)C1.C[Mg+].[Br-]>CCCC[N+](CCCC)(CCCC)CCCC.[Br-].ClCCl.O.C1COCC1>[CH2:42]([O:41][CH2:40][CH2:39][N:7]([C:8]1[S:9][C@H:10]2[O:16][C@H:15]([C@@H:17]([OH:18])[CH3:50])[C@@H:14]([O:19][CH2:20][C:21]3[CH:22]=[CH:23][C:24]([O:27][CH3:28])=[CH:25][CH:26]=3)[C@H:13]([O:29][CH2:30][C:31]3[CH:32]=[CH:33][C:34]([O:37][CH3:38])=[CH:35][CH:36]=3)[C@H:11]2[N:12]=1)[C:6](=[O:49])[O:5][C:1]([CH3:4])([CH3:2])[CH3:3])[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1

Participants

9

Reactant 4

HCID 67184N-bromobutanimideHCID 2724126TempoHCID 69082482HCID 69082482, compoundHCID 178418689HCID 178418689, compound

Product 1

HCID 69085611HCID 69085611, compound

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 134 (1.5 g, 2.2 mmol), KHCO3 (970 mg, 9.7 mmol), TBAB (70 mg, 0.2 mmol), TEMPO (31 mg, 0.2 mmol) in dichloromethane (50 mL) and H2O (10 mL) was added NBS (423 mg, 2.4 mmol) at 0° C. After stirred for 30 minutes at room temperature, the reaction was diluted with water (50 mL) and the aqueous layer was extracted with dichloromethane (2×30 mL). The combined organic layers was dried over anhydrous sodium sulfate, and concentrated under vacuum to give crude 135, which was dissolved into THF (20 mL). To the solution of 135 in THF was added MeMgBr (3 mL, 6 mmol, 2M in THF) at room temperature. After 1 hr, the reaction mixture was quenched with saturated aqueous NH4Cl solution (10 mL) and extracted with ethyl acetate (4×20 mL). The combined organic layer was washed with brine (2×20 mL), dried over anhydrous sodium sulfate and concentrated under vacuum. The crude residue was purified by a silica gel column, eluted with 10%-20% ethyl acetate in petroleum ether to afford 136 (0.95 g, 63%, two epimers, the ratio was 1:4 determined by 1H NMR) as a light yellow syrup. (ES, m/z) [M+H]+ 709.0; 1H NMR (300 MHz, CDCl3) δ 7.15-7.38 (m, 9H), 6.79-6.92 (m, 4H), 6.11 (m, 1H), 4.50-4.55 (m, 4H), 4.49 (s, 2H), 4.31-4.33 (m, 1H), 4.05-4.06 (m, 1H), 3.83-3.90 (m, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 3.54-3.66 (m, 2H), 3.31-3.52 (m, 3H), 3.11-3.15 (m, 1H) 1.54 (s, 9H), 1.12 (d, J=1.8 Hz, 3H).

Workup

  1. extractionthe aqueous layer was extracted with dichloromethane (2×30 mL)
  2. dry with materialThe combined organic layers was dried over anhydrous sodium sulfate
  3. concentrationconcentrated under vacuum
  4. customto give crude 135, which
  5. waitAfter 1 hr
  6. customthe reaction mixture was quenched with saturated aqueous NH4Cl solution (10 mL)
  7. extractionextracted with ethyl acetate (4×20 mL)
  8. washThe combined organic layer was washed with brine (2×20 mL)
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated under vacuum
  11. customThe crude residue was purified by a silica gel column
  12. washeluted with 10%-20% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-78b12202d0694913adf79629fa9b0523
Source dataset
uspto-grants-2014_12
Patent number
US08901087B2

Reaction notes

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