Pentane → {4-[(Bicyclo[2.2.1]hept-5-en-2-yl)methoxy]phenyl}(diphenyl)phosphane

HRID 249635

Reaktionsgleichung

Reaktionsgleichung von HRID 249635
I[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH:10]2[CH2:15][CH:14]3[CH2:16][CH:11]2[CH:12]=[CH:13]3)=[CH:4][CH:3]=1.CCCCC.[C:22]1([P:28]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[Si](C)(C)C)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>C1(C)C=CC=CC=1.CC#N.CC#N.Cl[Pd]Cl>[CH:11]12[CH2:16][CH:14]([CH:13]=[CH:12]1)[CH2:15][CH:10]2[CH2:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([P:28]([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[CH:3][CH:4]=1

Komponenten

6

Edukt 3

HCID 8003PentaneHCID 140190Diphenyl(trimethylsilyl)phosphineHCID 219893005-[(4-Iodophenoxy)methyl]bicyclo[2.2.1]hept-2-ene

Produkt 1

HCID 21989303{4-[(Bicyclo[2.2.1]hept-5-en-2-yl)methoxy]phenyl}(diphenyl)phosphaneAusbeute 14,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6093782Bis(acetonitrile)dichloropalladiumKatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

Bis(acetonitrile)dichloropalladium(II) (1 mmol) was placed in a Schlenk flask, stoppered with a septum and evacuated and purged with nitrogen three times. To this flask was then added a solution of 8 (0.038 mol) in 100 mL of anhydrous toluene and 9.6 g of diphenyl(trimethylsilyl)phosphine. The resulting deep purple solution was heated at 70° C. overnight, then cooled to room temperature and the solvent evaporated under reduced pressure. The residue was chromatographed on a column of silica gel using first hexane and then 9:1 hexane ethyl acetate as eluent to collect the product. After evaporation of the solvent, the product 9 (10 g), a mixture of endo and exo isomers, was obtained as white gummy material. Addition of 50 mL of hot pentane to this compound resulted in the separation of white crystalline compound (2.1 g). 1H NMR (500 MHz, 25° C., CDCl3): δ (endo isomer, ˜85%) 7.30 (m, 12H, Ar—H), 6.88 (m, 2H, Ar—H), 6.18 (m, 1H, olefinic), 5.98 (m, 1H, olefinic), 3.72 (m, 1H, nor-CH2), 3.57 (m 1H, nor-CH2), 3.04 (br s 1H), 2.88 (br s, 1H), 2.53 (m, 1H), 1.92 (m, 1H), 1.51 (d, |J|=8.0 Hz), 1.32 (d, |J|=8.2 Hz, 1H), 0.65 (m, 1H); (exo isomer, partial) 6.92 (m, 2H, Ar—H), 4.05 (m, 1H), 3.88 (m, 1H). 31P{1H} NMR (200 MHz, 25° C., CDCl3): δ−6.57

Aufarbeitung

  1. customevacuated
  2. custompurged with nitrogen three times
  3. temperaturecooled to room temperature
  4. customthe solvent evaporated under reduced pressure
  5. customThe residue was chromatographed on a column of silica gel using first hexane
  6. custom9:1 hexane ethyl acetate as eluent to collect the product
  7. customAfter evaporation of the solvent
  8. additionthe product 9 (10 g), a mixture of endo and exo isomers
  9. customwas obtained as white gummy material

Quellen und Nachweise

ORD-Eintrag
ord-adaa6c42efa3426d8e0abfecd0dd64d0
Quelldatensatz
uspto-grants-2011_01
Patentnummer
US07862860B2

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