Imidazole → Methyl 2-(benzyloxy)-5-((1R)-2-bromo-1-{[tert-butyl(dimethyl)silyl]oxy]ethyl)benzoate

HRID 1866501Notes

Reaction equation

HRID 1866501 reaction equation
[CH2:1]([O:8][C:9]1[CH:18]=[CH:17][C:16]([C@@H:19]([OH:22])[CH2:20][Br:21])=[CH:15][C:10]=1[C:11]([O:13][CH3:14])=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CN=C1.[Si:28](Cl)([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29]>CN(C1C=CN=CC=1)C.CN(C)C=O>[CH3:14][O:13][C:11](=[O:12])[C:10]1[CH:15]=[C:16]([C@@H:19]([O:22][Si:28]([C:31]([CH3:34])([CH3:33])[CH3:32])([CH3:30])[CH3:29])[CH2:20][Br:21])[CH:17]=[CH:18][C:9]=1[O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 795ImidazoleHCID 28928tert-Butyldimethylsilyl chlorideHCID 11003029(R)-Methyl 2-(benzyloxy)-5-(2-bromo-1-hydroxyethyl)benzoate

Product 1

HCID 57438683Methyl 2-(benzyloxy)-5-((1R)-2-bromo-1-{[tert-butyl(dimethyl)silyl]oxy]ethyl)benzoateYield 97.3%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of methyl 2-(benzyloxy)-5-[(1R)-2-bromo-1-hydroxyethyl]benzoate (71.05 g, 195 mmol), imidazole (18.52 g, 272 mmol), tert-butyldimethylsilyl chloride (32.23 g, 214 mmol) and 4-(N,N-dimethylamino)pyridine (0.44 g, 3.6 mmol) in N,N-dimethylformamide (270 ml) was left to stir at room temperature under a nitrogen atmosphere for a period of 24 hours. The solvent was removed in vacuo and the residue partitioned between ethyl acetate (500 ml) and water (500 ml). The organic phase was separated and washed with 2N hydrochloric acid (2-fold 500 ml), saturated aqueous sodium bicarbonate (2-fold 500 ml) saturated sodium chloride (500 ml), dried (magnesium sulfate) and the solvent removed in vacuo to give the title compound as a colourless oil (91.0 g). 1H NMR (400 MHz, CDCl3): δ=7.81 (1H, bs), 7.51-7.30 (6H, m), 7.01 (1H, d), 5.19 (2H, s), 4.85-4.82 (1H, m), 3.91 (3H, s), 3.48-3.39 (2H, m), 0.90 (9H, s), 0.11 (3H, s), -0.08 (3H, s) ppm. LRMS (electrospray): m/z [M+Na]+ 501/503.

Workup

  1. customThe solvent was removed in vacuo
  2. customthe residue partitioned between ethyl acetate (500 ml) and water (500 ml)
  3. customThe organic phase was separated
  4. washwashed with 2N hydrochloric acid (2-fold 500 ml), saturated aqueous sodium bicarbonate (2-fold 500 ml) saturated sodium chloride (500 ml)
  5. dry with materialdried (magnesium sulfate)
  6. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-18dcd57c4ea94a8a9576cac66d851c7e
Source dataset
uspto-grants-2009_12
Patent number
US07629358B2

Reaction notes

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