Triphenylphosphine → (R)-2-[2,6-Dibromo-4-(dibenzothiophen-1-yl)-phenoxy]-3-phenyl-propionic acid methyl ester

HRID 611742Notes

Reaction equation

HRID 611742 reaction equation
CCOC(/N=N/C(OCC)=O)=O.[Br:13][C:14]1[CH:19]=[C:18]([C:20]2[C:28]3[C:27]4[CH:29]=[CH:30][CH:31]=[CH:32][C:26]=4[S:25][C:24]=3[CH:23]=[CH:22][CH:21]=2)[CH:17]=[C:16]([Br:33])[C:15]=1[OH:34].O[C@@H:36]([CH2:41][C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1)[C:37]([O:39][CH3:40])=[O:38].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC=CC=1.CCOCC>[CH3:40][O:39][C:37](=[O:38])[C@H:36]([O:34][C:15]1[C:14]([Br:13])=[CH:19][C:18]([C:20]2[C:28]3[C:27]4[CH:29]=[CH:30][CH:31]=[CH:32][C:26]=4[S:25][C:24]=3[CH:23]=[CH:22][CH:21]=2)=[CH:17][C:16]=1[Br:33])[CH2:41][C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=1

Participants

7

Reactant 4

HCID 11776Triphenylphosphine2×HCID 5289077(S)-methyl 2-hydroxy-3-phenylpropanoate2×HCID 5462977Diethyl azodicarboxylate2×HCID 99326102,6-Dibromo-4-(dibenzothiophen-1-yl)-phenol

Product 1

HCID 54334532(R)-2-[2,6-Dibromo-4-(dibenzothiophen-1-yl)-phenoxy]-3-phenyl-propionic acid methyl esterYield 85,301.898%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

Diethylazodicarboxylate (DEAD, 0.077 mL, 1.15 mmol) was added to a stirred, room temperature suspension of 2,6-Dibromo-4-(dibenzothiophen-1-yl)-phenol (0.250 g, 0.576 mmol), (S)-2-hydroxy-3-phenylpropionic acid, methyl ester (0.208 g, 1.15 mmol), triphenylphosphine (0.302 g, 1.15 mmol) in benzene (3 mL) under a dry nitrogen atmosphere. Dissolution occurred and the solution was heated in an 80° C. oil bath for 16 h. More diethylazodicarboxylate (DEAD, 0.039 mL, 0.576 mmol), (S)-2-hydroxy-3-phenylpropionic acid, methyl ester (0.104 g, 0.576 mmol) and triphenylphosphine (0.151 g, 0.576 mmol) were added and the solution was stirred an additional 4 h. Upon cooling to room temperature, the reaction mixture was diluted with ether and silica gel was added. The reaction mixture was concentrated and the silica adsorbate was flash chromatographed (98:2 petroleum ether:ethyl acetate) to provide the title compound as a white solid (0. 293 g, 85%): NMR (CDCl3): δ 7.89 (dd, J=8, 1 Hz, 1H), 7.85 (ddd., J=8, 1, 1 Hz, 1H), 7.64 (d, J=2 Hz, 1H), 7.63 (d, J=2 Hz, 1H), 7.47 (dd, J=9, 8 Hz, 2H), 7.41-7.17 (m, 8H), 5.13 (dd, J=8, 6 Hz, 1H), 3.71 (s, 3H), 3.55 (dd, J=7, 4 Hz, 1H), 3.53 (dd, J=8, 4 Hz, 1H); MS (EI): [M+], 2 bromine isotope pattern, 594 (20%), 596 (40%) 598 (25%); Anal. Calc. for C28H20Br2O3S: C, 56.39, H, 3.38, N, 0.00. Found: C, 56.27, H, 3.21, N, 0.09.

Workup

  1. dissolutionDissolution
  2. temperatureUpon cooling to room temperature
  3. additionwas added
  4. concentrationThe reaction mixture was concentrated
  5. customchromatographed (98:2 petroleum ether:ethyl acetate)

Sources & evidence

ORD record
ord-4bd47b18da3249c587db2baadeba6040
Source dataset
uspto-grants-1999_12
Patent number
US06001867

Reaction notes

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