Triphenylphosphine → 9-((3aS,4R,6R,6aR)-6-(azidomethyl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)-6-chloro-9H-purine

HRID 2040611Notes

Reaction equation

HRID 2040611 reaction equation
[Cl:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[C@H:11]1[C@@H:15]2[O:16][C:17]([CH3:20])([CH3:19])[O:18][C@@H:14]2[C@@H:13]([CH2:21]O)[CH2:12]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.C1C=CC(OP(OC2C=CC=CC=2)([N:65]=[N+:66]=[N-:67])=O)=CC=1>C1COCC1>[N:65]([CH2:21][C@@H:13]1[C@H:14]2[O:18][C:17]([CH3:20])([CH3:19])[O:16][C@H:15]2[C@H:11]([N:6]2[CH:5]=[N:4][C:3]3[C:7]2=[N:8][CH:9]=[N:10][C:2]=3[Cl:1])[CH2:12]1)=[N+:66]=[N-:67]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 123414Diphenylphosphoryl azideHCID 10064860((3aR,4R,6R,6aS)-6-(6-chloro-9H-purin-9-yl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)methanol

Product 1

HCID 866661059-((3aS,4R,6R,6aR)-6-(azidomethyl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)-6-chloro-9H-purine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture of ((3aR,4R,6R,6aS)-6-(6-chloro-9H-purin-9-yl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)methanol (7.9 g, 24 mmol) and polymer-supported triphenylphosphine (3 mmol/g loading; 11 g, 34 mmol) in THF (100 mL) was cooled to 0° C. (ice/brine bath) and treated dropwise with diisopropyl azodicarboxylate (6.7 mL, 34 mmol). The tan slurry was stirred for 15 min, and treated dropwise with a solution of diphenylphosphonic azide (7.3 mL, 34 mmol) in THF (24 mL). The brown reaction mixture was stirred for 18.5 h as the ice bath expired; HPLC indicated conversion to the desired product. At 21.5 h the reaction mixture was filtered, the solids were washed with CH2Cl2, and the filtrate was concentrated in vacuo. The red-brown residue was taken up in CH2Cl2 (300 mL) and washed with saturated aqueous NaHCO3 (1×100 mL), water (1×100 mL), and brine (1×150 mL). The separated organic layer was dried (Na2SO4) and concentrated in vacuo to afford a red-orange oil. Purification by column chromatography (7×16 cm silica; 0-10% acetone/CH2Cl2) afforded the title compound (4.82 g, 57%) as a yellow oil/foam: MS (ESI+) for C14H16ClN7O2 m/z 350.1 (M+H)+; MS (ESI−) for C14H16ClN7O2 m/z 394.1 (M+HCO2)−.

Sources & evidence

ORD record
ord-5d6e02f8092d4d22a57c6e629af21e67
Source dataset
uspto-grants-2013_11
Patent number
US08580762B2

Reaction notes

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