Tetrabutylammonium Fluoride → 4-N-Benzoyl-3'-O-azidomethyl-5-[3-(2,2,2-trifluoroacetamido)-prop-1-ynyl]-2'-deoxycytidine

HRID 2273463Notes

Reaction equation

HRID 2273463 reaction equation
[C:1]([NH:9][C:10]1[C:34]([C:35]#[C:36][CH2:37][NH:38][C:39](=[O:44])[C:40]([F:43])([F:42])[F:41])=[CH:33][N:13]([C@@H:14]2[O:32][C@H:22]([CH2:23][O:24][Si](C(C)(C)C)(C)C)[C@@H:16]([O:17][CH2:18][N:19]=[N+:20]=[N-:21])[CH2:15]2)[C:12](=[O:45])[N:11]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[C:1]([NH:9][C:10]1[C:34]([C:35]#[C:36][CH2:37][NH:38][C:39](=[O:44])[C:40]([F:42])([F:41])[F:43])=[CH:33][N:13]([C@@H:14]2[O:32][C@H:22]([CH2:23][OH:24])[C@@H:16]([O:17][CH2:18][N:19]=[N+:20]=[N-:21])[CH2:15]2)[C:12](=[O:45])[N:11]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 866136144-N-Benzoyl-5'-O-(tert-butyldimethylsilyl)-3'-O-azidomethyl-5-[3-(2,2,2-trifluoroacetamido)-prop-1-ynyl]-2'-deoxycytidine

Product 1

HCID 866136134-N-Benzoyl-3'-O-azidomethyl-5-[3-(2,2,2-trifluoroacetamido)-prop-1-ynyl]-2'-deoxycytidine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The starting material (15) (140 mg, 0.22 mmol) was dissolved in THF (7.5 ml). TBAF (1M soln. in THF, 0.25 ml) was added slowly and stirred for 2 h at room temperature. Volatile material removed under reduced pressure to yield a brown gel that was purified by flash chromatography (EtOAc:DCM 7:3) to yield the desired product (16) as a light coloured crystalline solid (0.9 g, 76%). 1H NMR (d6 DMSO): δ2.16 (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), 5.32 (s, 1H, 5′ OH), 5.99 (m, 1H, H-1′), 7.37 (m, 2H, Ph), 7.50 (m, 2H, Ph), 7.81 (d, 1H, J=7.35 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 C22H20F3N7O6 535.44. found 534.

Workup

  1. customVolatile material removed under reduced pressure
  2. customto yield a brown gel that
  3. customwas purified by flash chromatography (EtOAc:DCM 7:3)

Sources & evidence

ORD record
ord-8fb4d9da78294aa388aa9ed5a9bbd64f
Source dataset
uspto-grants-2015_09
Patent number
US09121060B2

Reaction notes

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