Triphenylphosphine → (S)-1-Bromo-4-fluoro-2-(pent-4-en-2-yloxy)benzene

HRID 1481998Notes

Reaction equation

HRID 1481998 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[OH:9].[CH3:10][C@@H:11](O)[CH2:12][CH:13]=[CH2:14].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.CCOCC>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[O:9][C@H:13]([CH2:12][CH:11]=[CH2:10])[CH3:14]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 27246002-Bromo-5-fluorophenolHCID 5363146Diisopropyl azodicarboxylateHCID 6999724(2R)-pent-4-en-2-ol

Product 1

HCID 118308842(S)-1-Bromo-4-fluoro-2-(pent-4-en-2-yloxy)benzeneYield 60%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-bromo-5-fluorophenol (1.46 g, 7.64 mmol, 1 equiv), (R)-pent-4-en-2-ol (0.94 mL, 9.17 mmol, 1.2 equiv), and PPh3 (2.40 g, 9.17 mmol, 1.2 equiv) in THF (26 mL) was added DIAD (1.78 mL, 9.17 mmol, 1.2 equiv). After stirring 2 h, the yellow solution was diluted with ether, washed with 1 N NaOH, dried (MgSO4), and concentrated in vacuo. The crude product was purified by flash column chromatography (hexane) to provide the product (1.18 g, 60%) as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.49 (dd, J=8.7, 6.3 Hz, 1H), 6.67 (dd, J=10.6, 2.8 Hz, 1H), 6.62-6.56 (m, 1H), 5.91 (ddt, J=17.1, 10.1, 7.1 Hz, 1H), 5.22-5.12 (m, 2H), 4.49-4.38 (m, 1H), 2.62-2.52 (m, 1H), 2.49-2.40 (m, 1H), 1.39 (d, J=6.1 Hz, 3H).

Workup

  1. washwashed with 1 N NaOH
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by flash column chromatography (hexane)

Sources & evidence

ORD record
ord-3e5c53ba5067489190c77171b5b662b8
Source dataset
uspto-grants-2016_08
Patent number
US09409922B2

Reaction notes

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