Methanol → (R)-1-(4-Benzyloxy-3-nitrophenyl)-2-bromoethanol

HRID 2188798Notes

Reaction equation

HRID 2188798 reaction equation
B.C1COCC1.[CH2:7]([O:14][C:15]1[CH:20]=[CH:19][C:18]([C:21](=[O:24])[CH2:22][Br:23])=[CH:17][C:16]=1[N+:25]([O-:27])=[O:26])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.CO>C1(C)C=CC=CC=1.C1COCC1>[CH2:7]([O:14][C:15]1[CH:20]=[CH:19][C:18]([C@@H:21]([OH:24])[CH2:22][Br:23])=[CH:17][C:16]=1[N+:25]([O-:27])=[O:26])[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

6

Reactant 3

HCID 887MethanolHCID 2723981Borane;tetrahydrofuranHCID 110894102-Bromo-1-(3-nitro-4-phenylmethoxyphenyl)ethanone

Product 1

HCID 10882679(R)-1-(4-Benzyloxy-3-nitrophenyl)-2-bromoethanol

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of BH3.THF in THF (1 M, 108.00 mL, 108.00 mmol) was added to a solution of 1-(4-benzyloxy-3-nitrophenyl)-2-bromoethanone (3) (63.30 g, 180.00 mmol) and R-methyl-CBS-oxazoborolidine (1 M in toluene, 36.00 mL, 36.00 mmol) in anhydrous THF (500 mL). The resulting reaction mixture was stirred at rt for 16 h. Methanol (250 mL) was then slowly added to quench the reaction. After removal of solvent by rotary evaporation, the resulting residue was purified by column chromatography (silica gel, a gradient of 70:30 to 100:0 dichloromethane/hexanes) to give the desired bromo alcohol 4 as a yellow, viscous oil (36.80 g, 75% yield): 1H NMR (500 MHz, CDCl3) δ 2.72 (d, 1H), 3.48 (dd, 1H), 3.59 (dd, 1H), 4.89 (m, 1H), 5.21 (s, 2H), 7.11 (d, 1H), 7.39 (m, 5H), 7.50 (dd, 1H), 7.87 (d, 1H).

Workup

  1. customThe resulting reaction mixture
  2. customto quench
  3. customthe reaction
  4. customAfter removal of solvent
  5. customby rotary evaporation
  6. customthe resulting residue was purified by column chromatography (silica gel

Sources & evidence

ORD record
ord-9ea758a8fb7d408d99d7f8580c8b806a
Source dataset
uspto-grants-2012_12
Patent number
US08324218B2

Reaction notes

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