Sodium Azide → tert-butyl ((1S,2R,3R,5S)-5-(3-((tert-butoxycarbonyl)amino)pyridin-4-yl)-2-azido-3-methylcyclohexyl)carbamate

HRID 879186

Reaktionsgleichung

Reaktionsgleichung von HRID 879186
CS(O[C@@H:6]1[C@@H:11]([CH3:12])[CH2:10][C@@H:9]([C:13]2[CH:18]=[CH:17][N:16]=[CH:15][C:14]=2[NH:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:8][C@H:7]1[NH:27][C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])(=O)=O.[N-:35]=[N+:36]=[N-:37].[Na+]>CN(C=O)C>[C:23]([O:22][C:20]([NH:19][C:14]1[CH:15]=[N:16][CH:17]=[CH:18][C:13]=1[C@H:9]1[CH2:8][C@@H:7]([NH:27][C:28](=[O:29])[O:30][C:31]([CH3:34])([CH3:33])[CH3:32])[C@@H:6]([N:35]=[N+:36]=[N-:37])[C@@H:11]([CH3:12])[CH2:10]1)=[O:21])([CH3:26])([CH3:25])[CH3:24].[C:23]([O:22][C:20]([NH:19][C:14]1[CH:15]=[N:16][CH:17]=[CH:18][C:13]=1[C@@H:9]1[CH2:8][C@H:7]([NH:27][C:28](=[O:29])[O:30][C:31]([CH3:34])([CH3:33])[CH3:32])[C@H:6]([N:35]=[N+:36]=[N-:37])[C@H:11]([CH3:12])[CH2:10]1)=[O:21])([CH3:26])([CH3:25])[CH3:24]

Komponenten

5

Edukt 2

HCID 33557Sodium AzideHCID 86705223(1R,2R,4R,6S)-2-(tert-butoxycarbonylamino)-4-(3-(tert-butoxycarbonylamino)pyridin-4-yl)-6-methylcyclohexyl methanesulfonate

Produkt 2

HCID 86705234tert-butyl ((1R,2S,3S,5R)-5-(3-((tert-butoxycarbonyl)amino)pyridin-4-yl)-2-azido-3-methylcyclohexyl)carbamateAusbeute 21 %HCID 86705235tert-butyl ((1S,2R,3R,5S)-5-(3-((tert-butoxycarbonyl)amino)pyridin-4-yl)-2-azido-3-methylcyclohexyl)carbamateAusbeute 22 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

To a solution of (+/−)-(1R,2R,4R,6S)-2-(tert-butoxycarbonylamino)-4-(3-(tert-butoxycarbonylamino)pyridin-4-yl)-6-methylcyclohexyl methanesulfonate (1.0 equiv.) in DMF (0.13 M) was added NaN3 (1.0 equiv.). The solution was submerged in an 80° C. oil bath and left stirring under Ar for 16 hrs. The solution was cooled to rt and left stirring under Ar overnight. The solution was partitioned between EtOAc and H2O. The organic layer was washed with Na2CO3(sat.), NaCl(sat.), dried over MgSO4, filtered, concentrated and purified by ISCO SiO2 chromatography. Purification was completed via SFC (15% IPA, 100 mL/min, IA column) to yield tert-butyl ((1R,2S,3S,5R)-5-(3-((tert-butoxycarbonyl)amino)pyridin-4-yl)-2-azido-3-methylcyclohexyl)carbamate (21% yield, 99% ee) and tert-butyl ((1S,2R,3R,5S)-5-(3-((tert-butoxycarbonyl)amino)pyridin-4-yl)-2-azido-3-methylcyclohexyl)carbamate (22% yield, 99% ee). LC/MS (m/z)=447.3 (MH+), Rt=0.86 min.

Aufarbeitung

  1. customwas submerged in an 80° C.
  2. waitleft
  3. waitleft
  4. stirringstirring under Ar overnight
  5. customThe solution was partitioned between EtOAc and H2O
  6. washThe organic layer was washed with Na2CO3(sat.), NaCl(sat.)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. custompurified by ISCO SiO2 chromatography
  11. customPurification

Quellen und Nachweise

ORD-Eintrag
ord-dc8833edbc944af2ac25153c6e91975e
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08987457B2

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