Dimethylformamide → (S)-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-3-[(S)-1-(4-trimethylsilylethynyl-phenyl)-ethyl]-[1,3]oxazinan-2-one

HRID 333911

Reaktionsgleichung

Reaktionsgleichung von HRID 333911
CCN(CC)CC.[CH3:8][Si:9]([C:12]#[CH:13])([CH3:11])[CH3:10].Br[C:15]1[CH:20]=[CH:19][C:18]([CH:21]([N:23]2[CH2:28][CH2:27][C@:26]([CH2:35][C:36]([OH:39])([CH3:38])[CH3:37])([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[O:25][C:24]2=[O:40])[CH3:22])=[CH:17][CH:16]=1.CN(C)C=O>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(OCC)(=O)C.O>[OH:39][C:36]([CH3:37])([CH3:38])[CH2:35][C@@:26]1([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[O:25][C:24](=[O:40])[N:23]([C@H:21]([C:18]2[CH:17]=[CH:16][C:15]([C:13]#[C:12][Si:9]([CH3:11])([CH3:10])[CH3:8])=[CH:20][CH:19]=2)[CH3:22])[CH2:28][CH2:27]1

Komponenten

9

Edukt 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 66869824(S)-3-[1-(4-bromo-phenyl)-ethyl]-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-[1,3]oxazinan-2-one

Produkt 1

HCID 66869815(S)-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-3-[(S)-1-(4-trimethylsilylethynyl-phenyl)-ethyl]-[1,3]oxazinan-2-one

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

CuI (0.18 g), Pd(PPh3)2Cl2 (0.33 g), and NEt3 (2.22 mL) were added successively to a flask charged with a stir bar, trimethylsilylacetylene (1.31 mL), (S)-3-[1-(4-bromo-phenyl)-ethyl]-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-[1,3]oxazinan-2-one (2.00 g), and N,N-dimethylformamide (15 mL) and kept at room temperature under argon atmosphere. The flask was tightly sealed and the mixture was heated to 90° C. The mixture was stirred at 90° C. overnight and then cooled to ambient temperature. Water (80 mL) and ethyl acetate (200 mL) were added and the resulting mixture was filtered over Celite. The organic phase of the filtrate was separated and washed with brine and dried (MgSO4). The solvent was evaporated and the residue was chromatographed on silica gel (cyclohexane/ethyl acetate 3:1->0:1) to afford the title compound as an oil. Yield: 0.27 g (34% of theory); LC-MS (Method 1): tR=4.27 min; Mass spectrum (ESI+): m/z=450 [M+H]+.

Aufarbeitung

  1. additioncharged with a stir bar
  2. customkept at room temperature under argon atmosphere
  3. customThe flask was tightly sealed
  4. temperaturecooled to ambient temperature
  5. filtrationthe resulting mixture was filtered over Celite
  6. customThe organic phase of the filtrate was separated
  7. washwashed with brine
  8. dry with materialdried (MgSO4)
  9. customThe solvent was evaporated
  10. customthe residue was chromatographed on silica gel (cyclohexane/ethyl acetate 3:1->0:1)

Quellen und Nachweise

ORD-Eintrag
ord-8d7fa0c896144992a1e9e69fae94dd81
Quelldatensatz
uspto-grants-2014_11
Patentnummer
US08883778B2

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