Adenine → N6-(N-methyl-2-pyrrolidin-ylidene)-9-[(1RS,4SR)-4-hydroxy-cyclopent-2-en-1-yl]adenine

HRID 1780756Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1780756
P(OC(C)C)(OC(C)C)OC(C)C.C([Li])CCC.CCCCCC.[CH3:25][N:26]1[CH2:30][CH2:29][CH2:28][C:27]1=[N:31][C:32]1[N:40]=[CH:39][N:38]=[C:37]2[C:33]=1[NH:34][CH:35]=[N:36]2.N1C(N)=C2C(N=CN2)=NC=1.[O:51]1[C:53]2[CH2:54][CH2:55][CH2:56][C:52]1=2>O1CCCC1.CC(O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN1CCCC1=O.CS(C)=O>[CH3:25][N:26]1[CH2:30][CH2:29][CH2:28][C:27]1=[N:31][C:32]1[N:40]=[CH:39][N:38]=[C:37]2[C:33]=1[N:34]=[CH:35][N:36]2[CH:55]1[CH2:56][CH:52]([OH:51])[CH:53]=[CH:54]1

Komponenten

12

Edukt 6

HCID 190AdenineHCID 8058HexaneHCID 8304Triisopropyl phosphiteHCID 19047329N6-(N-methyl-pyrrolidin-ylidene)adenineHCID 22121731HCID 22121731, VerbindungHCID 178418339Butyllithium

Produkt 1

HCID 67878693N6-(N-methyl-2-pyrrolidin-ylidene)-9-[(1RS,4SR)-4-hydroxy-cyclopent-2-en-1-yl]adenineAusbeute 27,1 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 167845palladium(II) acetateKatalysatorHCID 679Dimethyl SulfoxideLösungsmittelHCID 3776IsopropanolLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 13387N-methyl-2-pyrrolidoneLösungsmittel

Versuchsvorschrift

224 mg (1 mmol) of palladium(II) acetate, 2.5 ml (10 mmol) of triisopropyl phosphite and 1.5 ml of 1.6 molar n-butyllithium solution in n-hexane (2 mmol) are brought together in 40 ml of dry tetrahydrofuran at 0° C. under inert nitrogen gas and the mixture is stirred. After addition of 30 ml of dry dimethylsulfoxide, 4.32 g (20 mmol) of N6 -(N-methyl-pyrrolidin-ylidene)adenine (prepared by reaction of adenine with the diethyl acetal of N-methyl-pyrrolid-2-one in 2-propanol; beige powder, melting point: 248°-251° C.) are added; a solution of 1.64 g (20 mmol) of epoxycyclopentene in 20 ml of dry tetrahydrofuran is then added dropwise in the course of one hour. The solution is stirred at room temperature for 12 hours and then concentrated and the residue is chromatographed over silica gel (methylene chloride/methanol 9/1). 1.62 g (27% of theory) of N6 -(N-methyl-2-pyrrolidin-ylidene)-9-[(1RS,4SR)-4-hydroxy-cyclopent-2-en-1-yl]adenine of melting point 135°-138° C. are obtained in a regiospecific manner. 1H NMR (270 MHz, d6 -DMSO), δ[ppm]: 8.42 (s, 1H), 8.16 (s, 1H), 6.20 (m, 1H), 6.00 (m, 1H), 5.50 (m, 1H), 5.46 (d, 1H), 4.73 (m, 1H), 3.50 (t, 2H), 3.04 (s, 3H), 2.90 (m, 1H), 2.85 (t, 2H), 1.97 (p, 2H), 1.74 (m, 1H). N6 -(N-Methyl-2-pyrrolidin-ylidene)-9-(cyclopent-1-en-3-on-1-yl)adenine of melting point 200°-205° C. is isolated as a by-product (20 mg, 0.3% of theory). 1H NMR (270 MHz, CDCl3), δ[ppm]: 8.64 (s, 1H), 8.13 (s, 1H), 7.19 (m, 1H), 3.53 (t, 2H), 3.34 (m, 2H), 3.20 (s, 3H), 3.07 (t, 2H), 2.65 (m, 2H), 2.10 (p, 2H).

Aufarbeitung

  1. additionbeige powder, melting point: 248°-251° C.) are added
  2. stirringThe solution is stirred at room temperature for 12 hours
  3. concentrationconcentrated
  4. customthe residue is chromatographed over silica gel (methylene chloride/methanol 9/1)

Quellen und Nachweise

ORD-Eintrag
ord-748dfcba98824a7cb055ff27a78ee47d
Quelldatensatz
uspto-grants-1997_05
Patentnummer
US05631259

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