Triphenylphosphine → (1S,4R)-4-[2-Chloro-6-(2,2-diphenyl-ethylamino)-purin-9-yl]-cyclopent-2-enol

HRID 1641881Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1641881
[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][NH:8]2)=[C:4]([NH:11][CH2:12][CH:13]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[N:3]=1.[H-].[Na+].CC([O:31][C@H:32]1[CH:36]=[CH:35][C@@H:34](O)[CH2:33]1)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:35]2[CH2:36][C@H:32]([OH:31])[CH:33]=[CH:34]2)=[C:4]([NH:11][CH2:12][CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[N:3]=1

Komponenten

6

Edukt 4

HCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 10154103rac-(1R,4S)-4-hydroxycyclopent-2-en-1-yl acetateHCID 178478404HCID 178478404, Verbindung

Produkt 1

HCID 86622638(1S,4R)-4-[2-Chloro-6-(2,2-diphenyl-ethylamino)-purin-9-yl]-cyclopent-2-enol

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 178418397HCID 178418397, VerbindungKatalysator

Versuchsvorschrift

(2-Chloro-9H-purin-6-yl)-(2,2-diphenyl-ethyl)-amine (12.92 g, 36.97 mmol) is placed in an oven-dried flask under an atmosphere of argon. Dry deoxygenated THF (100 mL) and dry DMSO (2 mL) are added and the suspension is cooled on an ice-bath. Sodium hydride 95% (0.89 g, 36.97 mmol) is then slowly added and the solution is stirred at room temperature for 30 minutes. (1S,4R)-cis 4-Acetoxy-2-cyclopenten-1-ol (5.00 g. 35.20 mmol) and triphenyl-phosphine (1.38 g, 5.28 mmol) are placed in an oven-dried flask under an atmosphere of argon. Dry deoxygenated THF (50 mL) is added. This solution is added to the anion solution via syringe. Tetrakis(triphenylphosphine)palladium(0) (2.03 g, 1.76 mmol) is then added and the reaction mixture is stirred at 50° C. for 3 hours. The reaction mixture is allowed to cool and the solvent is removed in vacuo. The residue is taken up in dichloromethane (50 ml) and poured into vigorously stirring diethyl ether (300 mL). The precipitate is filtered off, the filtrate is taken and the solvent is removed in vacuo to give the title compound. 1H nmr (CDCl3, 400 MHz); 7.65 (m, 1H), 7.35-7.15 (m, 10H), 6.35 (m, 1H), 5.90 (m, 1H), 5.80 (m, 1H), 5.50 (m, 1H), 5.25 (d, 1H), 4.85 (t, 1H), 4.35 (t, 1H), 4.25 (m, 2H), 2.95 (m, 1H), 2.15 (d, 1H), MS (ES+) m/e 432 (MH+).

Aufarbeitung

  1. customDry
  2. customdeoxygenated THF (100 mL) and dry DMSO (2 mL)
  3. additionare added
  4. temperaturethe suspension is cooled on an ice-bath
  5. customDry
  6. customdeoxygenated THF (50 mL)
  7. additionis added
  8. additionThis solution is added to the anion solution via syringe
  9. stirringthe reaction mixture is stirred at 50° C. for 3 hours
  10. temperatureto cool
  11. customthe solvent is removed in vacuo
  12. additionpoured into vigorously stirring diethyl ether (300 mL)
  13. filtrationThe precipitate is filtered off
  14. customthe solvent is removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-b1685ecfb0894a60bd5385ca2e312516
Quelldatensatz
uspto-grants-2012_02
Patentnummer
US08114877B2

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