Réaction #1994283

Équation de réaction

( 35 )

3′-O-Allyl-5-iodo-2′-deoxyuridine

triethylamine

propargyltrifluoroacetamide

→

crystals

Rendement 95.4%

3′-O-Allyl-5-[3-(2,2,2-trifluoroacetamido)-prop-1-ynyl]-2′-deoxyuridine

Rendement 95.4%

Solvants

DMF

Conditions de réaction

Traitement

1. 1
   AutreThe reaction was quenched
2. 2
   workup.ADDITIONby adding MeOH (10 ml), DCM (10 ml) and bicarbonate dowex
3. 3
   workup.STIRRINGThe mixture was stirred for 30 min
4. 4
   Filtrationfiltered
5. 5
   AutreThe solvents were removed under vacuum
6. 6
   Autrethe crude product was purified by chromatography on silica (EtOAc: petrol 3:7 to 7:3)

Mode opératoire

To a solution of (35) (400 mg, 1.0 mmol) in dry DMF (10 ml) was added CuI (38 mg, 20 μmol) and triethylamine (300 μl, 2.0 mmol). The propargyltrifluoroacetamide (453 mg, 3.0 mmol) was added drop wise, followed by Pd(PPh3)4 (110 mg, 9.5 μmol). The reaction was stirred for 16 h in the dark. The reaction was quenched by adding MeOH (10 ml), DCM (10 ml) and bicarbonate dowex. The mixture was stirred for 30 min and then filtered. The solvents were removed under vacuum and the crude product was purified by chromatography on silica (EtOAc: petrol 3:7 to 7:3). The product was isolated as slightly yellow crystals (398 mg, 95%). 1H NMR (d6 DMSO) δ 2.25-2.43 (m, 2H, H-2′), 3.65-3.76 (m, 2H, H-5′), 4.07-4.17 (m, 3H, H-4′, CH2), 4.21-4.23 (m, 1H, H-3′), 4.34 (d, J=5.5 Hz, 2H, CH2N), 5.25-5.27 (m, 2H, ═CH2, OH), 5.38 (dd, J=1.83, 17.3 Hz, 1H, ═CH2), 5.96-6.06 (m, 1H, ═CH), 6.17 (t, J=6.9 Hz, 1H, H-1′), 8.29 (s, 1H, H-6), 10.17 (t, J=5.5 Hz, 1H, NHTFA), 11.78 (s, 1H, NH). Mass (−ve electrospray) calcd for C17H18F3N3O6 417.11. Found 416.

Source