6-Oxabicyclo[3.1.0]hex-2-ene → HCID 10422292, compound

HRID 1885364Notes

Reaction equation

HRID 1885364 reaction equation
[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][NH:8]2)=[C:4]([Cl:11])[N:3]=1.[CH:12]12[O:17][CH:16]1[CH2:15][CH:14]=[CH:13]2>CS(C)=O.O1CCCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:13]2[CH2:12][C@H:16]([OH:17])[CH:15]=[CH:14]2)=[C:4]([Cl:11])[N:3]=1

Participants

6

Reactant 2

HCID 1655746-Oxabicyclo[3.1.0]hex-2-eneHCID 1785084356-chloro-1H-purin-2-amine

Product 1

HCID 10422292HCID 10422292, compound

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 679Dimethyl SulfoxideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 2-amino-6-chloro-9H-purine (4.0 g, 23.7 mmol) in dry dimethylsulfoxide (40 mL) at room temperature under N2 is added tetrakis(triphenylphosphine)palladium(O) (0.27 g, 0.23 mmol) and the mixture is stirred for 2 minutes. The solution is cooled to 0° C. and a solution of 6-oxa-bicyclo[3.1.0]hex-2-ene (2.1 g, 25.6 mmol) in dry tetrahydrofuran (20 mL) is added over 15 minutes. The resulting yellow solution is allowed to warm to ambient temperature (about 15°-30° C.) over 3 hours and stirred overnight (about 16 h). The clear, yellow solution is evaporated to a viscous oil which is taken up in dichloromethane (50 mL) and filtered through a small pad of Celite (trademark of Manville Products Corp. for infusorial earth filter aid). The solvent is evaporated and the residue is purified by silica gel chromatography using i) ethyl acetate followed by ii) 10:1 ethyl acetate:methanol as eluent to give cis-(±)-4-(2-amino-6-chloro-9H-purin-9-yl)-2-cyclo-penten-1-ol as a white solid, 5.14 g (86%). M.pt. 160°-162° C. 1H nmr: δ7.83 (s, 1H), 6.34 (dt, J1 =5.5 Hz, J2 =2 Hz, 1H), 5.85 (dd, J1 =5.5 Hz, 1H), 5.34 (d, J=10 Hz, 1H), 5.26 (dq, J1 =9 Hz, J2 =2 Hz, 1H), 5.12 (br s, 2H), 4.85 (br t, J=9 Hz, 1H), 2.97 (ddd, J1 =15 Hz, J2 =9 Hz, J3 =7 Hz, 1H), 2.13 (br d, J=15 Hz, 1H).

Workup

  1. temperatureto warm to ambient temperature (about 15°-30° C.) over 3 hours
  2. stirringstirred overnight (about 16 h)
  3. customThe clear, yellow solution is evaporated to a viscous oil which
  4. filtrationfiltered through a small pad of Celite (trademark of Manville Products Corp. for infusorial earth filter aid)
  5. customThe solvent is evaporated
  6. customthe residue is purified by silica gel chromatography

Sources & evidence

ORD record
ord-474c41c5073d48c9b7c26607c065b1f7
Source dataset
uspto-grants-1992_09
Patent number
US05144034

Reaction notes

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