Triphenylphosphine → (S)-4,5-difluoro-2-(pent-4-en-2-yloxy)benzaldehyde

HRID 921129

Reaktionsgleichung

Reaktionsgleichung von HRID 921129
[F:1][C:2]1[C:9]([F:10])=[CH:8][C:5]([CH:6]=[O:7])=[C:4]([OH:11])[CH:3]=1.[CH3:12][C@@H:13](O)[CH2:14][CH:15]=[CH2:16].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.CCOCC>[F:1][C:2]1[C:9]([F:10])=[CH:8][C:5]([CH:6]=[O:7])=[C:4]([O:11][C@H:15]([CH2:14][CH:13]=[CH2:12])[CH3:16])[CH:3]=1

Komponenten

7

Edukt 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 6999724(2R)-pent-4-en-2-olHCID 154345534,5-Difluoro-2-hydroxybenzaldehyde

Produkt 1

HCID 118307018(S)-4,5-difluoro-2-(pent-4-en-2-yloxy)benzaldehydeAusbeute 9,05 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of 4,5-difluoro-2-hydroxybenzaldehyde (1.0 g, 6.33 mmol) in THF (14 ml) were added (R)-(−)-pent-4-en-2-ol (1.090 g, 12.65 mmol) and triphenylphosphine (2.157 g, 8.22 mmol). DIAD (1.599 ml, 8.22 mmol) was added dropwise (exotherm) and the mixture was stirred at rt. After 1.5 h, the mixture was diluted with Et2O and washed with 1N NaOH followed by water (3×'s) then brine, dried (Na2SO4), filtered and concentrated. The yellow oil was purified by flash chromatography (Biotage; 0%-100% EtOAc/hexane; 20 CV) to give (S)-4,5-difluoro-2-(pent-4-en-2-yloxy)benzaldehyde (0.1295 g, 0.572 mmol, 9.05% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 10.36 (d, J=3.2 Hz, 1H), 7.76-7.55 (m, 1H), 6.83 (dd, J=11.9, 6.0 Hz, 1H), 6.04-5.67 (m, 1H), 5.23-5.06 (m, 2H), 4.48 (sxt, J=6.0 Hz, 1H), 2.71-2.35 (m, 2H), 1.41 (d, J=6.1 Hz, 3H).

Aufarbeitung

  1. washwashed with 1N NaOH
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe yellow oil was purified by flash chromatography (Biotage; 0%-100% EtOAc/hexane; 20 CV)

Quellen und Nachweise

ORD-Eintrag
ord-4b29f591b603425e81dc27f63be7a1ef
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09273067B2

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