Triacetoxyperiodinane → t-butyl (1R)-1-(4-(2-methylpentyloxy)phenyl)-2-oxoethylcarbamate

HRID 1874634Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1874634
[OH:1][CH2:2][C@H:3]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH:12]([CH3:16])[CH2:13][CH2:14][CH3:15])=[CH:6][CH:5]=1.C(=O)(O)[O-].[Na+].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.OS([O-])=O.[Na+]>ClCCl>[CH3:16][CH:12]([CH2:13][CH2:14][CH3:15])[CH2:11][O:10][C:7]1[CH:6]=[CH:5][C:4]([C@@H:3]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:22])([CH3:21])[CH3:23])[CH:2]=[O:1])=[CH:9][CH:8]=1

Komponenten

6

Edukt 4

HCID 159087TriacetoxyperiodinaneHCID 516892Sodium Bicarbonate2×HCID 23665763Sodium BisulfiteHCID 67433195t-butyl (1R)-2-hydroxy-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate

Produkt 1

HCID 86658401t-butyl (1R)-1-(4-(2-methylpentyloxy)phenyl)-2-oxoethylcarbamateAusbeute 64,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

A solution of t-butyl (1R)-2-hydroxy-1-(4-(2-methylpentyloxy)phenyl)ethylcarbamate (500 mg, 1.48 mmol) prepared according to the procedure described in example 1, in dichloromethane (10 mL) was treated with sodium bicarbonate (622 mg, 7.41 mmol) and Dess-Martin Periodinane (1.26 g, 2.96 mmol) at room temperature. The mixture was stirred at room temperature under N2 for 1.5 h. The reaction mixture was placed in an ice-water bath and a 1:1 mixture of saturated aqueous NaHCO3 solution and saturated NaHSO3 solution (4 mL) was added and the cooling bath was removed and the mixture was stirred for 5 min at room temperature. The reaction mixture was transferred to a separatory funnel containing saturated aqueous NaHCO3 solution (20 mL). The aqueous layer was extracted with ethyl acetate (3×25 mL). The combined organic layers were washed with brine (20 mL), dried over MgSO4, filtered and concentrated. The residue was purified by column chromatography on silica gel (10%→15% ethyl acetate in hexanes, 25 g column) to afford t-butyl (1R)-1-(4-(2-methylpentyloxy)phenyl)-2-oxoethylcarbamate (318 mg, 64% yield) as a colorless oil which was stored in the freezer until used in the next step: 1H NMR (400 MHz, DMSO-d6) δ 9.48 (s, 1H), 7.76 (d, J=7.6 Hz, 1H), 7.23 (d, J=8.6 Hz, 2H), 6.93 (d, J=8.6 Hz, 2H), 5.11 (d, J=7.6 Hz, 1H), 3.82 (dd, J=9.6, 6.0 Hz, 1H), 3.73 (dd, J=9.3, 6.5 Hz, 1H), 1.82-1.92 (m, 1H), 1.40 (s, 9H), 1.25-1.49 (m, 3H), 1.11-1.22 (m, 1H), 0.96 (d, J=6.8 Hz, 3H), 0.88 (t, J=7.1 Hz, 3H); LRMS (ESI) m/e 279.2 [(M-t-Bu)+, calcd for C15H21NO4 279.1].

Aufarbeitung

  1. customThe reaction mixture was placed in an ice-water bath
  2. additionwas added
  3. customthe cooling bath was removed
  4. stirringthe mixture was stirred for 5 min at room temperature
  5. customThe reaction mixture was transferred to a separatory funnel
  6. additioncontaining saturated aqueous NaHCO3 solution (20 mL)
  7. extractionThe aqueous layer was extracted with ethyl acetate (3×25 mL)
  8. washThe combined organic layers were washed with brine (20 mL)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe residue was purified by column chromatography on silica gel (10%→15% ethyl acetate in hexanes, 25 g column)

Quellen und Nachweise

ORD-Eintrag
ord-44cc3ddc1c6a415d9fbbd4b496ef63e4
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08304577B2

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