Phosphonium, (2-methoxy-2-oxoethyl)triphenyl-, bromide (1:1) → methyl (E)-3-[3-bromo-5-(1-cyanocyclopropyl)phenyl]prop-2-enoate

HRID 384072

Reaction equation

[Br-].[CH3:2][O:3][C:4](=[O:25])[CH2:5][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[Br:36][C:37]1[CH:38]=[C:39]([C:45]2([C:48]#[N:49])[CH2:47][CH2:46]2)[CH:40]=[C:41]([CH:43]=O)[CH:42]=1>C1COCC1>[Br:36][C:37]1[CH:42]=[C:41](/[CH:43]=[CH:5]/[C:4]([O:3][CH3:2])=[O:25])[CH:40]=[C:39]([C:45]2([C:48]#[N:49])[CH2:47][CH2:46]2)[CH:38]=1

Participants

Conditions

Temperature: -25 °C

Procedure

To a suspension of (2-methoxy-2-oxo-ethyl)-triphenyl-phosphonium bromide (1.502 g, 3.618 mmol) in THF (15 mL) under nitrogen at room temperature was added LHMDS in THF (3.358 mL of 1 M, 3.358 mmol) dropwise. The mixture was stirred for 10 mins then cooled to −25° C. 1-(3-bromo-5-formyl-phenyl)cyclopropane-1-carbonitrile (500 mg, 1.999 mmol) was dissolved in 1 mL of THF and added to the reaction. The reaction was allowed to warm to room temperature over 1 hour. The reaction was quenched with MeOH (2 mL) and then partitioned between ethyl acetate and brine. The aqueous was extracted with ethyl acetate and dried, filtered and concentrated. The crude product was purified on silica (Companion, 24 g) eluting with 1-20% EtOAc:Petrol ether to give methyl (E)-3-[3-bromo-5-(1-cyanocyclopropyl)phenyl]prop-2-enoate as a yellow solid (594 mg, 97%).

Workup

additionadded to the reaction
temperatureto warm to room temperature over 1 hour
customThe reaction was quenched with MeOH (2 mL)
custompartitioned between ethyl acetate and brine
extractionThe aqueous was extracted with ethyl acetate
customdried
filtrationfiltered
concentrationconcentrated
customThe crude product was purified on silica (Companion, 24 g)
washeluting with 1-20% EtOAc

Sources & evidence

ORD record: ord-7cee1abc5af14b87a6eed0dc1efcdd95
Source dataset: uspto-grants-2013_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08367697B2

Linked notes

Loading…