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

HRID 724713Notes

Reaction equation

HRID 724713 reaction equation
[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

Participants

4

Reactant 1

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

Product 1

HCID 11596601Methyl (2S)-2-[(benzyloxy)carbonyl]amino-3-(4-bromo-3-methylphenyl)propanoateYield 83.3%

Reagents, catalysts & solvents 2

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

Procedure

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.

Workup

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

Sources & evidence

ORD record
ord-d16d8de212384be5ac12c67fcd9d1aa8
Source dataset
uspto-grants-2006_11
Patent number
US07141596B2

Reaction notes

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