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Ammonium Chloride → (2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-carbamoyl-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627121
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Reaktionsgleichung

Reaktionsgleichung von HRID 627121
[CH2:1]([O:4][N:5]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C@H:6]1[CH2:11][N:10]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C@H:9]([CH2:19][OH:20])[CH:8]=[C:7]1[CH2:21][O:22][CH3:23])[CH:2]=[CH2:3].I([O-])(=O)(=O)=O.[Na+].OS([O-])=O.[Na+].C(O[N:46](C(OC(C)(C)C)=O)[C@H]1CN(C(OC(C)(C)C)=O)[C@H](C(O)=O)C=C1COC)C=C.[Cl-].[NH4+].CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CCN(C(C)C)C(C)C>CC#N.C(OCC)(=O)C.CN(C=O)C>[CH2:1]([O:4][N:5]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C@H:6]1[CH2:11][N:10]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C@H:9]([C:19](=[O:20])[NH2:46])[CH:8]=[C:7]1[CH2:21][O:22][CH3:23])[CH:2]=[CH2:3]
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Komponenten

11

Edukt 7

HCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 23665763Sodium BisulfiteHCID 23667635Sodium periodate
HCID 89851341
(2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-(hydroxymethyl)-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate
2×
HCID 89852905(2S,5R)-5-(allyloxy(tert-butoxycarbonyl)amino)-1-(tert-butoxycarbonyl)-4-(methoxymethyl)-1,2,5,6-tetrahydropyridine-2-carboxylic acid

Produkt 1

HCID 89852023(2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-carbamoyl-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylateAusbeute 43,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6228DimethylformamideLösungsmittelHCID 6342AcetonitrileLösungsmittelHCID 8857Ethyl AcetateLösungsmittel2×

Versuchsvorschrift

To a stirred solution of (2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-(hydroxymethyl)-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 72, 8.82 g, 20.58 mmol) in 100 mL MeCN at 0° C., was added sodium periodate (19.37 g, 90.56 mmol). Then 12 mL of the stock oxidation solution was added. The suspension was then stirred at rt for 2d. An additional 16 mL the above stock solution was added and stirred for 2 more days. The mixture was diluted with 150 mL ethyl acetate, 50 mL 1M pH 7 buffer, and 50 mL 2M NaHSO3. The aqueous was extracted with 20 mL ethyl acetate. The ethyl acetate layer was then washed with brine. The aqueous layer was checked by LCMS and found containing desired carboxylic acid. The aqueous layer was then extracted with 50 mL ethyl acetate and washed with brine. The combined organic layers was dried over MgSO4, filtered and concentrated to afford a yellow dry film, (crude 7.11 g, 78%) which was used directly without further purification. To a stirred solution of (2S,5R)-5-(allyloxy(tert-butoxycarbonyl)amino)-1-(tert-butoxycarbonyl)-4-(methoxymethyl)-1,2,5,6-tetrahydropyridine-2-carboxylic acid (crude, 7.11 g, 16.07 mmol), ammonium chloride (1.719 g, 32.14 mmol), HATU (12.22 g, 32.14 mmol) in DMF (50.0 mL) at rt, was added DIPEA (8.31 g, 64.27 mmol). After stirring at rt for 1 hr, 100 mL EtOAc was added. The organic layer was washed with water, brine. The residue was purified by silica gel column (0-100% Hex/EA) to afford the desired product (3.07 g, 43.3%) as an off-white solid.

Aufarbeitung

  1. additionThen 12 mL of the stock oxidation solution was added
  2. extractionThe aqueous was extracted with 20 mL ethyl acetate
  3. washThe ethyl acetate layer was then washed with brine
  4. additionfound containing desired carboxylic acid
  5. extractionThe aqueous layer was then extracted with 50 mL ethyl acetate
  6. washwashed with brine
  7. dry with materialThe combined organic layers was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford a yellow dry film
  11. custom(crude 7.11 g, 78%) which was used directly without further purification
  12. stirringAfter stirring at rt for 1 hr
  13. washThe organic layer was washed with water, brine
  14. customThe residue was purified by silica gel column (0-100% Hex/EA)

Quellen und Nachweise

ORD-Eintrag
ord-3752e13d3e464af3b92b724b5d90a003
Quelldatensatz
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09309245B2

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