Acetic Acid → 9-(4-Thio-2,3-dideoxy-D-ribofuranosyl)-6-chloropurine

HRID 653987Notes

Reaction equation

HRID 653987 reaction equation
[Si]([O:18][CH2:19][C@H:20]1[S:24][CH:23]([N:25]2[CH:33]=[N:32][C:31]3[C:26]2=[N:27][CH:28]=[N:29][C:30]=3[Cl:34])[CH2:22][CH2:21]1)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.C(O)(=O)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1>[CH:23]1([N:25]2[CH:33]=[N:32][C:31]3[C:26]2=[N:27][CH:28]=[N:29][C:30]=3[Cl:34])[S:24][C@H:20]([CH2:19][OH:18])[CH2:21][CH2:22]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 2724141Tetrabutylammonium FluorideHCID 151260999-(5-O-t-Butyldiphenylsilyl-4-thio-2,3-dideoxy-D-ribofuranosyl)-6-chloropurine

Product 1

HCID 151261019-(4-Thio-2,3-dideoxy-D-ribofuranosyl)-6-chloropurine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 11 (0.315 g, 0.62 mmol), acetic acid (30 μL, 0.63 mmol) and tetrabutylammonium fluoride (1 M in THF, 0.65 mL, 0.65 mmol) in 3 mL THF was stirred for 10 minutes under nitrogen. The solvent was removed in vacuo and the residue flash chromatographed with dichloromethane followed by 19:1 chloroform/methanol to give 0.164 g (98%) of the anomers. The anomers were separated by centrifugal chromatography with 19:1 chloroform/methanol: yield of β-anomer 10 mg; mp. 125°-128° C.; [α]D25 +2.5° (c=0.1 CH3OH); FAB MS 271 (M+H)+ ; 1H NMR (CDCl3) δ 9.0 (s, 1, H-2), 8.8 (s, 1, H-8), 6.3 (m, 1, 5'-OH), 3.8 (m, 1, 5'-H), 3.65 (m, 2, 4'-H, 5'-H), 2.6 (m, 1, 2'-H), 2.45 (m, 1, 2'-H), 2.2 (m, 1, 3'-H), 2.0 (m, 1, 3'-H).

Workup

  1. customThe solvent was removed in vacuo
  2. customthe residue flash chromatographed with dichloromethane
  3. customto give 0.164 g (98%) of the anomers
  4. customThe anomers were separated by centrifugal chromatography with 19:1 chloroform/methanol

Sources & evidence

ORD record
ord-ec60d8e46a3c4edd8bbd66b77c924074
Source dataset
uspto-grants-1992_07
Patent number
US05128458

Reaction notes

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