反応 #1994279

反応方程式

Cyclohexene

material ( 14 )

4-N-Benzoyl-5′-O-(tert-butyldimethylsilyl)-3′-O-methylthiomethyl-5-[3-(2,2,2-trifluoroacetamido)-prop-1-ynyl]-2′-deoxycytidine

Sodium azide

→

desired product

収率 55.0%

4-N-Benzoyl-5′—O-(tert-butyldimethylsilyl)-3′-O-azidomethyl-5-[3-(2,2,2-trifluoroacetamido)-prop-1-ynyl]-2′-deoxycytidine

収率 55.0%

溶媒

DMF

DCM

反応条件

後処理

1. 1
   workup.ADDITIONwas added
2. 2
   workup.STIRRINGthe mixture stirred for 1 h at 0° C
3. 3
   その他Volatiles were removed by evaporation
4. 4
   その他to yield a light brown solid that
5. 5
   workup.STIRRINGstirred for 2.5 h at room temperature
6. 6
   洗浄eluted with EtOAc
7. 7
   その他the volatiles removed by high vacuum evaporation
8. 8
   その他The resulting brown gel was purified by flash chromatography (petroleum ether:EtOAc 4:1 to 2:1)

実験手順

The starting material (14) (1.65 g, 2.99 mmol) was dissolved in DCM (18 ml) and cooled to 0° C. Cyclohexene (1.5 ml, 14.95 mmol) and SO2Cl2 (0.72 ml, 8.97 mmol) were added and stirred 1 h in ice bath. TLC indicated starting material still to be present whereupon a further aliquot of SO2Cl2 (0.24 ml) was added and the mixture stirred for 1 h at 0° C. Volatiles were removed by evaporation to yield a light brown solid that was redissolved in 18 ml of dry DMF (18 ml) under N2. Sodium azide (0.97 g, 14.95 mmol) was then added to the solution and stirred for 2.5 h at room temperature. The reaction mixture was passed through a pad of silica and eluted with EtOAc and the volatiles removed by high vacuum evaporation. The resulting brown gel was purified by flash chromatography (petroleum ether:EtOAc 4:1 to 2:1) to yield the desired product as a white crystalline solid (15) (0.9 g, 55%). 1H NMR (d6 DMSO): δ 0.00 (s, 6H, CH3), 0.78 (s, 9H, tBu), 2.16 (m, 1H, H-2′), 2.22 (m, 1H, H-2′), 3.70 (d, 1H, J=11.5 Hz, H-5′), 3.75 (d, 1H, J=11.3 Hz, H-5′), 4.01 (m, 1H, H-4′), 4.10 (m, 1H, CH2NH), 4.23 (m, 1H, H-3′), 4.76 (s, 2H, CH2S), 5.99 (m, 1H, H-1′), 7.37 (m, 2H, Ph), 7.50 (m, 2H, Ph), 7.81 (d, 1H, J=7.4 Hz, Ph), 7.95 (s, 1H, H-6), 9.78 (br s, 1H, NHCH2), 12.64 (br s, 1H, NH). Mass (−ve electrospray) calcd for C28H34F3N7O6Si 649.71. Found 648.2

出典