2-Cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-[4-cyclopropyl-5-(3-isobutylcyclobutyl)isoxazol-3-yl]valerate

HRID 1912054Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1912054
[Si:1]([O:18][CH2:19][CH2:20][CH:21]([C:30]1[C:34](I)=[C:33]([CH:36]2[CH2:39][CH:38]([CH2:40][CH:41]([CH3:43])[CH3:42])[CH2:37]2)[O:32][N:31]=1)[CH2:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:44]1(B2OC(C)(C)C(C)(C)O2)[CH2:46][CH2:45]1>CN(C=O)C>[Si:1]([O:18][CH2:19][CH2:20][CH:21]([C:30]1[C:34]([CH:44]2[CH2:46][CH2:45]2)=[C:33]([CH:36]2[CH2:39][CH:38]([CH2:40][CH:41]([CH3:43])[CH3:42])[CH2:37]2)[O:32][N:31]=1)[CH2:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

4

Edukt 2

HCID 27580152-Cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 71127322tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-[4-iodo-5-(3-isobutylcyclobutyl)isoxazol-3-yl]valerate

Produkt 1

HCID 71127323tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-[4-cyclopropyl-5-(3-isobutylcyclobutyl)isoxazol-3-yl]valerateAusbeute 61,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-[4-iodo-5-(3-isobutylcyclobutyl)isoxazol-3-yl]valerate (37.44 g), 2-cyclopropyl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (17.58 g) and DMF (262 mL) were mixed. After the resulting solution was degassed by bubbling argon, tripotassium phosphate (33.32 g) and PdCl2(PPh3)2 (3.67 g) were added to the mixture. The mixture was stirred at 80° C. overnight. After water (200 mL) was poured into the reaction, the resultant precipitate was removed by filtration and the filtrate was extracted with toluene (600 mL). The organic layer was washed with water (200 mL×2, 320 mL) and brine (160 mL), then dried over sodium sulfate. The sodium sulfate was filtered off and the filtrate was concentrated in vacuo. After an addition of silica gel (45 g) and ethyl acetate/hexane=1/20 (400 mL) to the residue, the mixture was stirred at RT. The silica gel was filtered off and the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (Eluent: ethyl acetate/hexane=1/80→1/60→1/50) to give the title compound (20.2 g).

Aufarbeitung

  1. customAfter the resulting solution was degassed
  2. customby bubbling argon, tripotassium phosphate (33.32 g) and PdCl2(PPh3)2 (3.67 g)
  3. additionwere added to the mixture
  4. additionAfter water (200 mL) was poured into the reaction
  5. customthe resultant precipitate was removed by filtration
  6. extractionthe filtrate was extracted with toluene (600 mL)
  7. washThe organic layer was washed with water (200 mL×2, 320 mL) and brine (160 mL)
  8. dry with materialdried over sodium sulfate
  9. filtrationThe sodium sulfate was filtered off
  10. concentrationthe filtrate was concentrated in vacuo
  11. additionAfter an addition of silica gel (45 g) and ethyl acetate/hexane=1/20 (400 mL) to the residue
  12. stirringthe mixture was stirred at RT
  13. filtrationThe silica gel was filtered off
  14. concentrationthe filtrate was concentrated in vacuo
  15. customThe residue was purified by silica gel column chromatography (Eluent: ethyl acetate/hexane=1/80→1/60→1/50)

Quellen und Nachweise

ORD-Eintrag
ord-eb02eacd94ae4be98066b1acc3a6d6d3
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08604069B2

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