2-Bromoethanol → HCID 86684665, compound

HRID 1504357Notes

Reaction equation

HRID 1504357 reaction equation
[Br:1][CH2:2][CH2:3][OH:4].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[NH:24]([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[C@H:25]([C:34]([O:36][CH3:37])=[O:35])[CH2:26][C:27]1[CH:32]=[CH:31][C:30](O)=[CH:29][CH:28]=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1>[Br:1][CH2:2][CH2:3][O:4][C:30]1[CH:29]=[CH:28][C:27]([CH2:26][C@H:25]([NH:24][C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[C:34]([O:36][CH3:37])=[O:35])=[CH:32][CH:31]=1

Participants

6

Reactant 4

HCID 108982-BromoethanolHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 7019130Boc-Tyr-OMe

Product 1

HCID 86684665HCID 86684665, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

2-Bromo-ethanol (0.61 mL, 8.03 mmol), followed by PPh3 (3.16 g, 12.05 mmol) was added to a solution of Boc-Tyr-OMe (2.85 g, 9.64 mmol) in anhydrous THF (50 mL). The mixture was cooled to 0° C. and DEAD (5.5 mL of 40% wt solution in toluene, 12.05 mmol) was added. The mixture was allowed to warm at room temperature and was stirred overnight. After the reaction was finished, the solvent was evaporated and the residue dissolved in EtOAc (100 mL) was washed with NaOH (0.1 M, 2×50 mL), followed by brine. The organic phase was dried over Na2SO4 and evaporated. The crude product was purified by flash column chromatography (SiO2, step-wise gradient from 2-40% EtOAc in Hexanes) to give 1A (1.61 g, 50%) as a white solid. 1H NMR (600 MHz, CDCl3): δ 7.04 (2H, d, J=8.4 Hz), 6.84 (2H, d, J=8.4 Hz), 4.96 (1H, d, J=7.8 Hz), 4.51-4.58 (1H, m), 4.27 (2H, t, J=6.6 Hz), 3.71 (3H, s), 3.62 (2H, t, J=6.6 Hz), 3.06 (1H, dd, J=13.8, 5.4 Hz), 3.00 (1H, dd, J=13.8, 5.4 Hz), 1.42 (9H, s); 13C NMR (150 MHz, CDCl3): δ 172.3, 157.2, 155.1, 130.4, 128.8, 114.8, 79.9, 67.9, 54.5, 52.2, 37.5, 29.1, 28.3; MS (ESI, m/z): 424 (M+Na)+.

Workup

  1. temperatureto warm at room temperature
  2. customthe solvent was evaporated
  3. dissolutionthe residue dissolved in EtOAc (100 mL)
  4. washwas washed with NaOH (0.1 M, 2×50 mL)
  5. dry with materialThe organic phase was dried over Na2SO4
  6. customevaporated
  7. customThe crude product was purified by flash column chromatography (SiO2, step-wise gradient from 2-40% EtOAc in Hexanes)

Sources & evidence

ORD record
ord-de0c5e1355c9413b8ea25cf6b6621de1
Source dataset
uspto-grants-2015_12
Patent number
US09212381B2

Reaction notes

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