Ammonium formate → Ammonium formate

HRID 1433294Notes

Reaction equation

HRID 1433294 reaction equation
[CH:1]([O-:3])=[O:2].[NH4+:4].C([O:12][C:13]1[CH:18]=[CH:17][C:16]([C@@H:19]([O:62][Si:63]([C:66]([CH3:69])([CH3:68])[CH3:67])([CH3:65])[CH3:64])[CH2:20][NH:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH:30]=[CH:31][C:32]2[CH:37]=[CH:36][C:35]([O:38]CC3C=CC=CC=3)=[C:34]([C@@H:46]([C:56]3[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=3)[CH2:47][CH2:48][N:49]([CH:53]([CH3:55])[CH3:54])[CH:50]([CH3:52])[CH3:51])[CH:33]=2)=[CH:15][C:14]=1[NH:70][S:71]([CH3:74])(=[O:73])=[O:72])C1C=CC=CC=1>CO.[OH-].[Pd+2].[OH-]>[Si:63]([O:62][C@H:19]([C:16]1[CH:17]=[CH:18][C:13]([OH:12])=[C:14]([NH:70][S:71]([CH3:74])(=[O:72])=[O:73])[CH:15]=1)[CH2:20][NH:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][C:32]1[CH:37]=[CH:36][C:35]([OH:38])=[C:34]([C@@H:46]([C:56]2[CH:57]=[CH:58][CH:59]=[CH:60][CH:61]=2)[CH2:47][CH2:48][N:49]([CH:50]([CH3:51])[CH3:52])[CH:53]([CH3:55])[CH3:54])[CH:33]=1)([C:66]([CH3:69])([CH3:67])[CH3:68])([CH3:65])[CH3:64].[CH:1]([O-:3])=[O:2].[NH4+:4]

Participants

6

Reactant 2

HCID 2723923Ammonium formateHCID 86616474N-{2-(benzyloxy)-5-[(1R)-2-{[10-{4-(benzyloxy)-3-[(1R)-3-(diisopropylamino)-1-phenylpropyl]phenyl}dec-9-en-1-yl]amino}-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl]phenyl}methanesulfonamide

Product 2

HCID 2723923Ammonium formateHCID 68934182N-(5-{(1R)-1-{[tert-butyl(dimethyl)silyl]oxy}-2-[(10-{3-[(1R)-3-(diisopropylamino)-1-phenylpropyl]-4-hydroxyphenyl}decyl)amino]ethyl}-2-hydroxyphenyl)methanesulfonamide

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolvent

Procedure

Palladium hydroxide (10% on carbon, 20 mg) was added to a stirred solution of ammonium formate (344 mg, 5.46 mmol) and N-{2-(benzyloxy)-5-[(1R)-2-{[10-{4-(benzyloxy)-3-[(1R)-3-(diisopropylamino)-1-phenylpropyl]phenyl}dec-9-en-1-yl]amino}-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl]phenyl}methanesulfonamide (Preparation 4, 90 mg, 0.091 mmol) in methanol (10 ml) at room temperature. The reaction was heated under reflux for 1 hour, cooled to room temperature and filtered through Arbocel™. The filtrate was collected and the solvent removed in vacuo to yield N-(5-{(1R)-1-{[tert-butyl(dimethyl)silyl]oxy}-2-[(10-{3-[(1R)-3-(diisopropylamino)-1-phenylpropyl]-4-hydroxyphenyl}decyl)amino]ethyl}-2-hydroxyphenyl)methanesulfonamide as a mixture with residual ammonium formate. LRMS: m/z 811 [M+H]+. This mixture was dissolved in tetrahydrofuran (4 ml) and methanol (2 ml) and triethylaminetrihydrofluoride (88 ul, 0.54 mmol) was added in one portion at room temperature. The reaction was stirred for 12 hours and the solvent removed under reduced pressure, the residue was dissolved in methanol (10 ml) and 880 ammonia (1 ml) and the solvent removed under reduced pressure. The residue was purified by column chromatography on silica gel eluting with dichloromethane:methanol:880 ammonia (80/20/2.0 by volume) to furnish the title compound as a glass, 35 mg.

Workup

  1. temperatureThe reaction was heated
  2. temperatureunder reflux for 1 hour
  3. filtrationfiltered through Arbocel™
  4. customThe filtrate was collected
  5. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-e5ec55cf2f4144ae971f1437cae6ccd5
Source dataset
uspto-grants-2009_11
Patent number
US07612084B2

Reaction notes

Loading…