Triphenylphosphine → (2R)-Methyl 2-(tert-butoxycarbonylamino)-(4-((S)-2-methyl-butoxy)-phenyl)acetate

HRID 1874638

Reaktionsgleichung

Reaktionsgleichung von HRID 1874638
[C:1]([O:5][C:6]([NH:8][C@H:9]([C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=1)[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:21][C@@H:22]([CH2:25][CH3:26])[CH2:23]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>O1CCCC1>[C:1]([O:5][C:6]([NH:8][C@H:9]([C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:21][C@@H:22]([CH3:23])[CH2:25][CH3:26])=[CH:16][CH:15]=1)[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Komponenten

6

Edukt 4

HCID 11776TriphenylphosphineHCID 2723602(S)-2-methyl-1-butanolHCID 5363146Diisopropyl azodicarboxylateHCID 10934864Methyl (2R)-2-{[(tert-butoxy)carbonyl]amino}-2-(4-hydroxyphenyl)acetate

Produkt 1

HCID 67438449(2R)-Methyl 2-(tert-butoxycarbonylamino)-(4-((S)-2-methyl-butoxy)-phenyl)acetateAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

A 0° C. solution of (R)-Methyl 2-(tert-butoxycarbonylamino)-2-(4-hydroxyphenyl)acetate (2.8 g, 10 mmol), (S)-2-methyl-1-butanol (1.1 mL, 10 mmol), triphenylphosphine (2.6 g, 10 mmol), and tetrahydrofuran (100 mL) was treated dropwise with diisopropylazodicarboxylate (1.9 mL, 10 mmol) via syringe. The resulting reaction mixture was allowed to warm to room temperature and maintained overnight. The reaction was concentrated and the residue was purified by column chromatography on silica gel (5%→10% ethyl acetate in hexanes) to afford (2R)-methyl 2-(tert-butoxycarbonylamino)-(4-((S)-2-methyl-butoxy)-phenyl)acetate (2.8 g, 80% yield) as a clear, colorless oil: 1H NMR (400 MHz, CDCl3) δ 7.27 (d, J=7.3 Hz, 2H), 6.88 (d, J=8.6 Hz, 2H), 5.49 (d, J=6.6 Hz, 1H), 5.26 (d, J=7.3 Hz, 1H), 3.81 (dd, J=9.1, 6.1 Hz, 1H), 3.73 (s, 3H), 3.69-3.76 (m, 1H), 1.86 (dq, J=13.1, 6.5 Hz, 1H), 1.52-1.61 (m, 1H), 1.45 (s, 9H), 1.22-1.33 (m, 2H), 1.02 (d, J=6.8 Hz, 3H), 0.95 (t, J=7.5 Hz, 3H); LRMS (ESI) m/e 352.2 [(M+H)+, calcd for C19H30NO5 352.5].

Aufarbeitung

  1. customThe resulting reaction mixture
  2. temperaturemaintained overnight
  3. concentrationThe reaction was concentrated
  4. customthe residue was purified by column chromatography on silica gel (5%→10% ethyl acetate in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-518e7f99b01748ab890b01504b8aa4a3
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08304577B2

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