Tetrabutylammonium Fluoride → (S)-4-(3-Hydroxy-2-methylpropyl)-6-methyl-4H-benzo[1,4]oxazin-3-one

HRID 1191375Notes

Reaction equation

HRID 1191375 reaction equation
[Si]([O:8][CH2:9][C@@H:10]([CH3:24])[CH2:11][N:12]1[C:17]2[CH:18]=[C:19]([CH3:22])[CH:20]=[CH:21][C:16]=2[O:15][CH2:14][C:13]1=[O:23])(C(C)(C)C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[OH:8][CH2:9][C@@H:10]([CH3:24])[CH2:11][N:12]1[C:17]2[CH:18]=[C:19]([CH3:22])[CH:20]=[CH:21][C:16]=2[O:15][CH2:14][C:13]1=[O:23]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 68909987(S)-4-[3-(tert-butyldimethylsilanyloxy)-2-methylpropyl]-6-methyl-4H-benzo[1,4]oxazin-3-one

Product 1

HCID 68908602(S)-4-(3-Hydroxy-2-methylpropyl)-6-methyl-4H-benzo[1,4]oxazin-3-one

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The compound (S)-4-[3-(tert-butyldimethylsilanyloxy)-2-methylpropyl]-6-methyl-4H-benzo[1,4]oxazin-3-one (101IS60-1) (1.0 g, 2.9 mmol) was dissolved in dry THF (12 mL) and TBAF (1.2 g, 3.8 mmol) was added. The reaction was stirred at rt overnight and the solution was concentrated under reduced pressure, the remaining oil was diluted with EtOAc (60 mL) and washed with brine (3×30 mL), dried (Na2SO4) filtered and concentrated under reduced pressure. The remaining oil was purified by flash chromatography (SiO2; Heptane/EtOAc 30:70) to yield an oil which crystallized upon standing (0.69 g, 76%). 1H NMR (CDCl3) δ 6.88 (d, J=8.4 Hz, 1H), 6.83-6.78 (m, 2H), 4.59 (brs 2H), 4.22 (dd J=10.0, 14.4 Hz), 3.57-3.38 (m, 3H), 2.9 (vbrs, 1H), 2.33 (s, 3H), 2.04 (m, 1H), 1.08 (d, J=7.2 Hz); 13C NMR (CDCl3) δ 165.7, 143.4, 132.3, 124.9, 117.1, 115.9, 67.6, 63.7, 43.5, 34.2, 21.3, 15.1.

Workup

  1. concentrationthe solution was concentrated under reduced pressure
  2. additionthe remaining oil was diluted with EtOAc (60 mL)
  3. washwashed with brine (3×30 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe remaining oil was purified by flash chromatography (SiO2; Heptane/EtOAc 30:70)
  8. customto yield an oil which
  9. customcrystallized

Sources & evidence

ORD record
ord-038af9c43708437b872809c6a2c9e09b
Source dataset
uspto-grants-2014_03
Patent number
US08680115B2

Reaction notes

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