Ammonia → (1S,3R)-benzyl 3-acetamido-2,2-dimethylcyclobutanecarboxylate

HRID 2179727Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2179727
C([C@@H:4]1[CH2:7][C@H:6]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[C:5]1([CH3:19])[CH3:18])(=O)C.[N-]=[N+]=[N-].[Na+].CS(O)(=O)=O.[NH3:29].[CH2:30]([CH2:33]OC)[O:31]C>>[C:30]([NH:29][C@@H:4]1[CH2:7][C@H:6]([C:8]([O:10][CH2:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[O:9])[C:5]1([CH3:18])[CH3:19])(=[O:31])[CH3:33]

Komponenten

6

Edukt 5

HCID 222AmmoniaHCID 6395Methanesulfonic AcidHCID 80711,2-DimethoxyethaneHCID 33557Sodium AzideHCID 58111012(1S,3R)-benzyl 3-acetyl-2,2-dimethylcyclobutanecarboxylate

Produkt 1

HCID 86650107(1S,3R)-benzyl 3-acetamido-2,2-dimethylcyclobutanecarboxylateAusbeute 82,2 %

Versuchsvorschrift

A stirred solution of (1S,3R)-benzyl 3-acetyl-2,2-dimethylcyclobutanecarboxylate (1.5 g, 5.76 mmol) in monoglyme (18.75 ml) at −45° C., NaN3 (1.12 g, 17.30 mmol), MeSO3H (10.5 ml), were added drop wise slowly and the reaction was allowed to stir at room temperature for about 48 hours. After completion of the reaction (monitored by TLC), the reaction mixture was neutralized with aqueous ammonia solution. Solvent was evaporated and diluted with DCM. Organic layer was washed with water, brine dried over Na2SO4. The solvent was evaporated under reduced pressure and the resulting crude purified by silica gel column (60/120 mesh, elution: 30% EtOAc in Hexane) to afford the title compound as off white solid. Wt: 1.3 g; Yield: 82.2%; 1H NMR (300 MHZ, CD3OD): δ 7.42-7.31 (m, 5H), 5.59 (d, 1H, J=5.7 Hz), 5.12 (s, 2H), 4.13 (q, 1H, J=9.3 Hz), 2.69-2.63 (m, 1H), 2.38-2.34 (m, 1H), 2.13-2.06 (m, 1H), 2.05 (s, 3H), 1.30 (s, 3H), 0.86 (s, 3H). Mass: [M+1]+ 276 (100%), [M+Na]+ 298 (66%); IR (KBr, cm−1): 3270, 2963, 2866, 1728, 1647, 1571, 1455, 1303, 1151, 1071, 1019, 961, 755, 742; M.R: 85.6° C.-97.5° C.

Aufarbeitung

  1. customAfter completion of the reaction (monitored by TLC)
  2. customSolvent was evaporated
  3. additiondiluted with DCM
  4. washOrganic layer was washed with water, brine
  5. dry with materialdried over Na2SO4
  6. customThe solvent was evaporated under reduced pressure
  7. customthe resulting crude purified by silica gel column (60/120 mesh, elution: 30% EtOAc in Hexane)

Quellen und Nachweise

ORD-Eintrag
ord-7784a036fad24a98a232ad1c7909d280
Quelldatensatz
uspto-grants-2015_06
Patentnummer
US09067966B2

Notizen zur Reaktion

Wird geladen…