Acetic Acid → N-(2-{9-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-(methoxymethyl)tetrahydro-2-furanyl]-6-[(2,2-diphenylethyl)amino]-9H-purin-2-yl}ethyl)-N-(1-ethylpropyl)amine

HRID 2268414Notes

Reaction equation

HRID 2268414 reaction equation
C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C.[NH2:19][CH2:20][CH2:21][C:22]1[N:30]=[C:29]2[C:25]([N:26]=[CH:27][N:28]2[C@H:31]2[C@H:35]([O:36][Si:37]([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38])[C@H:34]([O:44][Si:45]([C:48]([CH3:51])([CH3:50])[CH3:49])([CH3:47])[CH3:46])[C@@H:33]([CH2:52][O:53][CH3:54])[O:32]2)=[C:24]([NH:55][CH2:56][CH:57]([C:64]2[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=2)[C:58]2[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=2)[N:23]=1.[CH2:70]([C:72]([CH2:74][CH3:75])=O)[CH3:71]>ClCCl.C(OCC)(=O)C>[Si:37]([O:36][C@@H:35]1[C@H:34]([O:44][Si:45]([C:48]([CH3:49])([CH3:50])[CH3:51])([CH3:47])[CH3:46])[C@@H:33]([CH2:52][O:53][CH3:54])[O:32][C@H:31]1[N:28]1[CH:27]=[N:26][C:25]2[C:29]1=[N:30][C:22]([CH2:21][CH2:20][NH:19][CH:72]([CH2:74][CH3:75])[CH2:70][CH3:71])=[N:23][C:24]=2[NH:55][CH2:56][CH:57]([C:58]1[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=1)[C:64]1[CH:65]=[CH:66][CH:67]=[CH:68][CH:69]=1)([C:40]([CH3:41])([CH3:42])[CH3:43])([CH3:39])[CH3:38]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 7288Ethyl ketone2×HCID 5049666Sodium triacetoxyborohydride2×HCID 69534061N-{2-(2-Aminoethyl)-9-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-(methoxymethyl)tetrahydro-2-furanyl]-9H-purin-6-yl}-N-(2,2-diphenylethyl)amine

Product 1

HCID 69534102N-(2-{9-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-(methoxymethyl)tetrahydro-2-furanyl]-6-[(2,2-diphenylethyl)amino]-9H-purin-2-yl}ethyl)-N-(1-ethylpropyl)amineYield 91.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Sodium triacetoxyborohydride (105 mg, 0.51 mmol) and glacial acetic acid (24 mg, 0.40 mmol) were added to a stirred solution of N-{2-(2-aminoethyl)-9-[(2R,3R,4R,5R)-3,4-bis{[tert-butyl(dimethyl)silyl]oxy}-5-(methoxymethyl)tetrahydro-2-furanyl]-9H-purin-6-yl}-N-(2,2-diphenylethyl)amine (250 mg, 0.34 mmol) (preparation 18) and diethyl ketone (58 mg, 0.68 mmol) in dichloromethane (15 ml) and the resulting mixture stirred under an atmosphere of nitrogen gas at room temperature overnight. Additional portions of diethyl ketone (30 mg, 0.35 mmol) and sodium triacetoxyborohydride (60 mg, 0.29 mmol) were then added and stirring continued at room temperature for a further 24 hr. The mixture was diluted with ethyl acetate (20 ml) and washed sequentially with saturated aqueous sodium hydrogen carbonate solution, brine and water. The organic phase was separated and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue purified by column chromatography on silica gel eluting with dichloromethane:methanol:ammonia (96:4:0.4) to give the title compound (250 mg) as a gum. MS: 803 (MH+).

Workup

  1. stirringstirring
  2. waitcontinued at room temperature for a further 24 hr
  3. washwashed sequentially with saturated aqueous sodium hydrogen carbonate solution, brine and water
  4. customThe organic phase was separated
  5. dry with materialdried with anhydrous sodium sulfate
  6. customThe solvent was removed under reduced pressure
  7. customthe residue purified by column chromatography on silica gel eluting with dichloromethane:methanol:ammonia (96:4:0.4)

Sources & evidence

ORD record
ord-76b3281e58304efb9171e3cb52836bd9
Source dataset
uspto-grants-2001_12
Patent number
US06326359B1

Reaction notes

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