Benzyl Bromide → HCID 11488850, compound

HRID 1356202Notes

Reaction equation

HRID 1356202 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:13][C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[C:16]([I:21])[CH:15]=1)[C:10]([OH:12])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].CCN(C(C)C)C(C)C.[CH2:31](Br)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.CCCCCC.CCOC(C)=O>CCOC(C)=O>[CH2:31]([O:11][C:10](=[O:12])[C@@H:9]([NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[CH2:13][C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[C:16]([I:21])[CH:15]=1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

Participants

6

Reactant 4

HCID 7498Benzyl BromideHCID 81531DiisopropylethylamineHCID 15545208N-(tert-Butoxycarbonyl)-3-iodo-L-tyrosineHCID 21226206Ethyl acetate hexane2×

Product 1

HCID 11488850HCID 11488850, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

(2S)-2-tert-Butoxycarbonylamino-3-(4-hydroxy-3-iodo-phenyl)-propionic acid (490 mg. 1.2 mmol) of Step A is stirred in EtOAc (3.6 mL) with DIEA (418 μL, 2.4 mmol) at RT under N2. Benzyl bromide (171 μL, 1.44 mmol) is then added and the reaction mixture is then heated to 90° C. overnight. TLC in 3/1 hexane/EtOAc shows complete consumption of starting material (ninhydrin positive) and the appearance of two higher rf spots. The reaction is cooled to RT, diluted with EtOAc and washed with 1N HCl (2×30 mL) and with saturated NaHCO3 (2×30 mL). The organics are dried (MgSO4), filtered and concentrated to provide a mixture of mono- and dibenzylated products. Flash chromatography (3:1 hexane/EtOAc) affords the title compound, (2S)-2-tert-butoxycarbonylamino-3-(4-hydroxy-3-iodo-phenyl)-propionic acid benzyl ester.

Workup

  1. customconsumption of starting material (ninhydrin positive)
  2. temperatureThe reaction is cooled to RT
  3. additiondiluted with EtOAc
  4. washwashed with 1N HCl (2×30 mL) and with saturated NaHCO3 (2×30 mL)
  5. dry with materialThe organics are dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto provide
  9. additiona mixture of mono- and dibenzylated products

Sources & evidence

ORD record
ord-a30a2d0ebd524706808224d26c80fdfd
Source dataset
uspto-grants-2003_07
Patent number
US06586467B2

Reaction notes

Loading…