1,4-Dibromobenzene → methyl (S)-3-(4-bromophenyl)-2-hydroxypropionate

HRID 910292

Reaction equation

C([Li])(C)(C)C.Br[C:7]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=1.[Cu](C#N)C#N.[C:19]([O:24][CH3:25])(=[O:23])[C@H:20]1[O:22][CH2:21]1.[Cl-].[NH4+]>CCCCC>[Br:13][C:10]1[CH:11]=[CH:12][C:7]([CH2:21][C@H:20]([OH:22])[C:19]([O:24][CH3:25])=[O:23])=[CH:8][CH:9]=1

Participants

Conditions

Temperature: -30 °C

Procedure

100 ml (170 mmol) of a 1.7 M solution of tert-butyllithium in pentane are added dropwise to a solution of 48 g (204 mmol) of 1,4-dibromobenzene in 160 ml of tert-butyl dimethyl ether, cooled to −30° C., followed by addition of 7.3 g (82 mmol) of copper cyanide. The reaction medium is stirred for 15 minutes and a solution of 6 ml (68 mmol) of (S)-methyl glycidate in 10 ml of tert-butyl dimethyl ether is then added. After stirring for 20 minutes at −30° C., the reaction medium is hydrolysed with 150 ml of saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic phase is washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and evaporated. The residue obtained is purified by chromatography on a column of silica eluted with heptane, and the polarity is then increased up to a 6/4 heptane/ethyl acetate mixture. 23.5 g (44%) of methyl 3-(4-bromophenyl)-2(S)-hydroxypropanoate are obtained.

Workup

stirringAfter stirring for 20 minutes at −30° C.
extractionextracted with ethyl acetate
washThe organic phase is washed with saturated aqueous sodium chloride solution
dry with materialdried over magnesium sulfate
filtrationfiltered
customevaporated
customThe residue obtained
customis purified by chromatography on a column of silica
washeluted with heptane
temperaturethe polarity is then increased up to a 6/4 heptane/ethyl acetate mixture

Sources & evidence

ORD record: ord-c044be1b64664c599a14b5eb357fd1ea
Source dataset: uspto-grants-2011_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08022079B2

Linked notes

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