Chlorotrimethylsilane → HCID 15126108, compound

HRID 653981

Reaction equation

HRID 653981 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.[NH:29]1[CH:36]=[CH:35][C:33]([NH2:34])=[N:32][C:30]1=[O:31].FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S([O-])(=O)=O.[K+].C[Si](N[Si](C)(C)C)(C)C.[Si](Cl)(C)(C)C.C([O-])(O)=O.[Na+]>C(#N)C.ClCCl>[Si:12]([O:11][CH2:10][C@H:8]1[S:9][C@@H:5]([N:29]2[CH:36]=[CH:35][C:33]([NH2:34])=[N:32][C:30]2=[O:31])[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

9

Reactant 6

HCID 6397ChlorotrimethylsilaneHCID 13838HexamethyldisilazaneHCID 516892Sodium BicarbonateHCID 151260981-O-Acetyl-5-O-t-butyldiphenylsilyl-4-thio-2,3-dideoxyribofuranoseHCID 23675274Potassium perfluorobutanesulfonateHCID 178418229Cytosine

Product 1

HCID 15126108HCID 15126108, compound

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

A mixture of 10 (0.26 g, 0.63 mmol), cytosine (0.105 g, 0.95 mmol), and potassium nonafluorobutanesulfonate (0.77 g, 2.3 mmol) was suspended in 12 mL dry acetonitrile under nitrogen. HMDS (0.135 mL, 0.63 mmol) and TMS-Cl (0.37 mL, 2.9 mmol) were added sequentially via syringe and the reaction stirred at 25° C. overnight. The reaction was poured into a mixture of 20 mL dichloromethane and 15 mL saturated NaHCO3 and shaken. The organic phase was dried (MgSO4) and concentrated in vacuo. The anomeric mixture was separated by preparative TLC with 7.5% MeOH/CHCl3 with an ammonia atmosphere: yield of β-anomer, 78 mg and 117 mg of the α-anomer to afford total yield of 195 mg (66.5%); FAB MS 466 (M+H)+ ; 1H NMR (CDCl3) of α/β anomer, δ 8.12 (d, 1, 6-H), 7.7 (m, 4, ArH), 7.4 (m, 6, ArH), 6.32 (m, 1, 1'-H), 5.9-5.3 (hump, 1, NH2), 5.75 (d, 1, 5-H), 5.45 (d, 1, 5-H), 3.75 (m, 3, 4'-Hα,β 's, 3'-Hα,β 's).

Workup

  1. stirringshaken
  2. dry with materialThe organic phase was dried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customThe anomeric mixture was separated by preparative TLC with 7.5% MeOH/CHCl3 with an ammonia atmosphere
  5. customyield of β-anomer, 78 mg and 117 mg of the α-anomer to afford total yield of 195 mg (66.5%)

Sources & evidence

ORD record
ord-e369a01e7e4949d5a42ef03f07094859
Source dataset
uspto-grants-1992_07
Patent number
US05128458

Linked notes

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