Tri-o-tolylphosphine → Ammonia

HRID 1433284Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1433284
[CH2:1]([N:9]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH:7]=[CH2:8].[CH2:24]([O:31][C:32]1[CH:37]=[CH:36][C:35](Br)=[CH:34][C:33]=1[C@@H:39]([C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)[CH2:40][CH2:41][N:42]([CH:46]([CH3:48])[CH3:47])[CH:43]([CH3:45])[CH3:44])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)C(C)C)(C)C.C(=O)([O-])O.[Na+]>C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C(OCC)(=O)C.C(#N)C>[NH3:9].[C:13]([O:12][C:10]([N:9]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]/[CH:7]=[CH:8]/[C:35]1[CH:36]=[CH:37][C:32]([O:31][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[C:33]([C@@H:39]([C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[CH2:40][CH2:41][N:42]([CH:43]([CH3:45])[CH3:44])[CH:46]([CH3:47])[CH3:48])[CH:34]=1)[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])=[O:11])([CH3:14])([CH3:15])[CH3:16]

Komponenten

10

Edukt 5

HCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 516892Sodium BicarbonateHCID 24885301(R)-3-(2-benzyloxy)-5-bromophenyl)-N,N-diisopropyl-3-phenylpropan-1-amineHCID 57933160Di-tert-butyl oct-7-en-1-ylimidodicarbonate

Produkt 2

HCID 222AmmoniaHCID 57933221di-tert-butyl[(7E)-8-{4-(benzyloxy)-3-[(1R)-3-(diisopropylamino)-1-phenylpropyl]phenyl}oct-7-en-1-yl]imidodicarbonate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 6342AcetonitrileLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

di-tert-butyl oct-7-en-1-ylimidodicarbonate (Preparation 48, 649 mg, 1.98 mmol), (3R)-3-[2-(benzyloxy)-5-bromophenyl]-N,N-diisopropyl-3-phenylpropan-1-amine (Prepared according to WO1994/11337, 560 mg, 1.16 mmol), palladium diacetate (27 mg, 0.12 mmol), tris(2-methylphenyl)phosphine (73 mg, 0.24 mmol) and N,N-diisopropylethylamine (0.304 ml, 1.75 mmol) were added to acetonitrile (6 ml) and the mixture was heated to 90° C. and left to stir overnight under nitrogen. Mixture was cooled and saturated aqueous sodium hydrogen carbonate and ethyl acetate were added. Organics separated and washed with saturated aqueous sodium hydrogen carbonate, brine, dried (magnesium sulphate) and the solvent removed in vacuo. The residue was purified by column chromatography on silica gel eluting with dichloromethane:methanol:880 ammonia (100/0/0 to 96/4/0.4 by volume) to furnish the title compound as a oil, 530 mg.

Aufarbeitung

  1. waitleft
  2. temperatureMixture was cooled
  3. customOrganics separated
  4. washwashed with saturated aqueous sodium hydrogen carbonate, brine
  5. dry with materialdried (magnesium sulphate)
  6. customthe solvent removed in vacuo
  7. customThe residue was purified by column chromatography on silica gel eluting with dichloromethane

Quellen und Nachweise

ORD-Eintrag
ord-6f12f1367def4b99b30b7f65ad290513
Quelldatensatz
uspto-grants-2009_11
Patentnummer
US07612084B2

Notizen zur Reaktion

Wird geladen…