3-Bromophenol → Methyl O-(3-bromophenyl)-N-triphenylmethyl-L-serinate

HRID 1265218Notes

Reaction equation

HRID 1265218 reaction equation
[OH:1][CH2:2][C@H:3]([NH:8][C:9]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]([O:6][CH3:7])=[O:5].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:47][C:48]1[CH:49]=[C:50](O)[CH:51]=[CH:52][CH:53]=1.CCOC(/N=N/C(OCC)=O)=O>C1(C)C=CC=CC=1>[Br:47][C:48]1[CH:53]=[C:52]([O:1][CH2:2][C@@H:3]([C:4]([O:6][CH3:7])=[O:5])[NH:8][C:9]([C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH:51]=[CH:50][CH:49]=1

Participants

6

Reactant 4

HCID 115633-BromophenolHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 7128367N-(Triphenylmethyl)-L-serine methyl ester

Product 1

HCID 11329766Methyl O-(3-bromophenyl)-N-triphenylmethyl-L-serinateYield 67.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Methyl (2S)-3-hydroxy-2-(triphenylmethylamino)propanoate (5.2 g , 14.4 mmol, 1 equiv; prepared according to Baldwin, J. E.; Spivey, A. C.; Schofield, C. J.; Sweeney, J. B. Tetrahedron 1993, 49, 6309) and triphenylphosphine (4.2 g, 15.8 mmol, 1.1 equiv) were dissolved in toluene (25 mL) at rt (room temperature). The reaction mixture was stirred for 30 min followed by addition of 3-bromo phenol (3.2 g, 18.7 mmol, 1.3 equiv) and DEAD (diethylazo dicarboxylate; 2.8 g, 15.8 mmol, 1.1 equiv) at rt. The reaction mixture was stirred at ambient temperature for 15 h while a white precipitate formed. The precipitate was filtered off and the solvents of the filtrate were removed in vacuuo. The remaining crude product was purified by flash chromatography (cyclohexanes/ethyl acetate 95:5) to give a white solid (5.2 g, 67.3%). 1H NMR (CDCl3, 200 MHz) δ 7.65-7.55 (m, 4 H); 7.41-7.12 (m, 9H); 6.70 (d, 2H); 4.20 (dd, 1H); 4.00 (dd, 1H); 3.75-3.60 (m, 1H); 3.73 (s, 3H); 2.87 (d, 1H).

Workup

  1. customprepared
  2. stirringThe reaction mixture was stirred at ambient temperature for 15 h while a white precipitate
  3. customformed
  4. filtrationThe precipitate was filtered off
  5. customthe solvents of the filtrate were removed in vacuuo
  6. customThe remaining crude product was purified by flash chromatography (cyclohexanes/ethyl acetate 95:5)

Sources & evidence

ORD record
ord-b39cc39780034a5592a9b4bc1d92010c
Source dataset
uspto-grants-2003_04
Patent number
US06545029B2

Reaction notes

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