Tributyl borate → 3-(1-Carboxy-ethyl)-phenyl boronic acid

HRID 2110704Notes

Reaction equation

HRID 2110704 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:8]([CH3:12])[C:9]([OH:11])=[O:10])[CH:5]=[CH:6][CH:7]=1.C([Li])(C)(C)C.[B:18](OCCCC)([O:24]CCCC)[O:19]CCCC>CCOCC>[C:9]([CH:8]([C:4]1[CH:3]=[C:2]([B:18]([OH:24])[OH:19])[CH:7]=[CH:6][CH:5]=1)[CH3:12])([OH:11])=[O:10]

Participants

5

Reactant 3

HCID 12712Tributyl borateHCID 127979542-(3-Bromophenyl)propanoic acid2×HCID 178418306HCID 178418306, compound

Product 1

HCID 576360703-(1-Carboxy-ethyl)-phenyl boronic acid

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of 2-(3-bromo-phenyl)-propionic acid [500 mg, 2.18 mmol, Intermediate (69)] in anhydrous ether (20 mL) is added tert-butyl lithium (1.7 M in pentane, 5.4 mL, 9.16 mmol) dropwise at −78° C. and this mixture is stirred for 30 minutes treated with tributyl borate (2.34 mL, 8.72 mmol). The reaction mixture is allowed to warm up to room temperature, stirred for 15 hours, diluted with ether, and quenched with 1 M H3PO4. After stirring for 30 minutes the ether layer is separated and extracted three times with 2 N sodium hydroxide (20 mL). The combined sodium hydroxide extracts are acidified with 6 N hydrochloric acid to pH=1 and extracted three times with ether (50 mL). The combined organic extracts are washed with brine, dried over sodium sulfate and concentrated to obtain 3-(1-carboxy-ethyl)-phenyl boronic acid [Intermediate (70)] as a solid, which is used without further purification.

Workup

  1. stirringstirred for 15 hours
  2. customquenched with 1 M H3PO4
  3. stirringAfter stirring for 30 minutes the ether layer
  4. customis separated
  5. extractionextracted three times with 2 N sodium hydroxide (20 mL)
  6. extractionextracted three times with ether (50 mL)
  7. washThe combined organic extracts are washed with brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-dc1c2514ad6a4b799824c01504e4743e
Source dataset
uspto-grants-2009_04
Patent number
US07517889B2

Reaction notes

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