Toluene → 9-(5-O-t-Butyldiphenylsilyl-4-thio-2,3-dideoxy-D-ribofuranosyl)-6-chloropurine

HRID 653979Notes

Reaction equation

HRID 653979 reaction equation
C(O[CH:5]1[S:9][C@H:8]([CH2:10][O:11][Si:12]([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:7][CH2:6]1)(=O)C.[Cl:29][C:30]1[N:38]=[CH:37][N:36]=[C:35]2[C:31]=1[NH:32][CH:33]=[N:34]2.C1(C)C=CC=CC=1.[Cl-].C([Al+]CC)C>C(#N)C>[Si:12]([O:11][CH2:10][C@H:8]1[S:9][CH:5]([N:34]2[CH:33]=[N:32][C:31]3[C:35]2=[N:36][CH:37]=[N:38][C:30]=3[Cl:29])[CH2:6][CH2:7]1)([C:25]([CH3:27])([CH3:26])[CH3:28])([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 53592776-ChloropurineHCID 151260981-O-Acetyl-5-O-t-butyldiphenylsilyl-4-thio-2,3-dideoxyribofuranoseHCID 16686102Diethyl aluminum chloride

Product 1

HCID 151260999-(5-O-t-Butyldiphenylsilyl-4-thio-2,3-dideoxy-D-ribofuranosyl)-6-chloropurine

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 10 (0.43 g, 1.04 mmol) and 6-chloropurine (0.24 g, 1.56 mmol) in 17 mL acetonitrile was cooled to 0° C. and a 1.8 M toluene solution of diethylaluminum chloride (0.59 mL, 1.06 mmol) was added over 1 minute. Stirring was continued at 0° C. for 5 minutes and at 25° C. for 10 minutes. The reaction mixture was quenched by pouring into a mixture of 20 mL dichloromethane and 10 mL saturated NaHCO3. The organic phase was dried (MgSO4) and concentrated in vacuo. The residue was flash chromatographed with 9:1 hexane/ethyl acetate followed by 4:1 hexane/ethyl acetate. Solvent removal gave a 1:1 α/β anomeric mixture: yield 0.315 g (59%); FAB MS 509 (M+H)+ ; 1H NMR (CDCl3) of β anomer, δ 8.7 (s, 1, H-2), 8.45 (s, 1, H-8), 7.7 (m, 4, ArH), 7.4 (m, 6, ArH), 6.27 (m, 1, 7'-H), 3.95 (m, 1, 5'-H), 3.85 (m, 2, 4'-H, 5'-H), 2.45 (m, 2, 2'-H's), 2.25 (m, 1, 3'-H), 1.85 (m, 1, 3'-H), 1.1 (s, 9, t-butyl).

Workup

  1. customThe reaction mixture was quenched
  2. additionby pouring into a mixture of 20 mL dichloromethane and 10 mL saturated NaHCO3
  3. dry with materialThe organic phase was dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customchromatographed with 9:1 hexane/ethyl acetate
  6. customSolvent removal
  7. customgave a 1:1 α/β anomeric mixture

Sources & evidence

ORD record
ord-0b61da0e21044f8487a325999904231f
Source dataset
uspto-grants-1992_07
Patent number
US05128458

Reaction notes

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