Methyl-2-[(benzyloxy)carbonyl]amino-3-(4-bromo-3-methylphenyl)acrylate → Methyl (2S)-2-[(benzyloxy)carbonyl]amino-3-(4-bromo-3-methylphenyl)propanoate

HRID 724713Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 724713
[CH3:1][O:2][C:3](=[O:25])[C:4]([NH:14][C:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:16])=[CH:5][C:6]1[CH:11]=[CH:10][C:9]([Br:12])=[C:8]([CH3:13])[CH:7]=1>C(O)C.[B-](F)(F)(F)F.COC1C([P@](CC[P@](C2C=CC=CC=2)C2C(OC)=CC=CC=2)C2C=CC=CC=2)=CC=CC=1.C1CC=CCCC=C1.[Rh]>[CH2:18]([O:17][C:15]([NH:14][C@@H:4]([CH2:5][C:6]1[CH:11]=[CH:10][C:9]([Br:12])=[C:8]([CH3:13])[CH:7]=1)[C:3]([O:2][CH3:1])=[O:25])=[O:16])[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Komponenten

4

Edukt 1

HCID 69597784Methyl-2-[(benzyloxy)carbonyl]amino-3-(4-bromo-3-methylphenyl)acrylate

Produkt 1

HCID 11596601Methyl (2S)-2-[(benzyloxy)carbonyl]amino-3-(4-bromo-3-methylphenyl)propanoateAusbeute 83,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 10930696(1Z,5Z)-cycloocta-1,5-diene;(R)-(2-methoxyphenyl)-[2-[(2-methoxyphenyl)-phenylphosphanyl]ethyl]-phenylphosphane;rhodium;tetrafluoroborateKatalysatorHCID 702EthanolLösungsmittel

Versuchsvorschrift

A solution of methyl-2-[(benzyloxy)carbonyl]amino-3-(4-bromo-3-methylphenyl)acrylate (10.4 g, 0.0257 mol) in ethanol (200 mL) was degassed with nitrogen. (R,R)-(−)-1,2-bis[(o-methoxyphenyl)(phenyl)phosphino]ethane(1,5-cyclooctadiene) rhodium (I) tetrafluroborate (194 mg, 257 μmol) was added to the reaction solution and nitrogen was bubble through. After five cycles of vacuum/H2, the reaction was heated at a pressure of 50 psi of hydrogen at room temperature. After 24 h, the solvent was removed under reduced pressure. The crude residue was purified by flash column chromatography to yield the desired product (8.7 g, 83%). 1H NMR (400 MHz, CD3OD): δ 7.40 (d, 1H), 7.3 (m, 5H), 7.13 (s, 1H), 6.91 (m, 1H), 5.00 (m, 2H), 4.42 (m, 1H), 3.70 (s, 3H), 3.09 (m, 1H), 2.84 (m, 1H), 2.32 (s, 3H); MF=C19H20BrNO4; LCMS found for C19H20BrNO4Na (M+Na)+: m/z=428, 430.

Aufarbeitung

  1. customwas bubble through
  2. customthe solvent was removed under reduced pressure
  3. customThe crude residue was purified by flash column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-d16d8de212384be5ac12c67fcd9d1aa8
Quelldatensatz
uspto-grants-2006_11
Patentnummer
US07141596B2

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