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2,2,2-Trifluoroethyl trifluoromethanesulfonate → tert-Butyl((5S,6R)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl)carbamate

HRID 706373
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 706373
[CH3:1][C@H:2]1[NH:7][C:6](=[O:8])[C@@H:5]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH2:4][C@H:3]1[C:17]1[C:22]([F:23])=[CH:21][CH:20]=[C:19]([F:24])[C:18]=1[F:25].C(O[Li])(C)(C)C.FC(F)(F)S(O[CH2:38][C:39]([F:42])([F:41])[F:40])(=O)=O.CN1C(=O)N(C)CCC1>C1COCC1>[CH3:1][C@H:2]1[N:7]([CH2:38][C:39]([F:42])([F:41])[F:40])[C:6](=[O:8])[CH:5]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:14])([CH3:15])[CH3:13])[CH2:4][C@H:3]1[C:17]1[C:22]([F:23])=[CH:21][CH:20]=[C:19]([F:24])[C:18]=1[F:25]
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Komponenten

6

Edukt 4

HCID 803662,2,2-Trifluoroethyl trifluoromethanesulfonateHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 89821838tert-Butyl ((3S,5S,6R)-6-methyl-2-oxo-5-(2,3,6-trifluorophenyl)piperidin-3-yl)carbamateHCID 178506942HCID 178506942, Verbindung2×

Produkt 1

HCID 89821792
tert-Butyl((5S,6R)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl)carbamate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 21 (10 g, 87% purity, 24.3 mmol) in THF (70 ml) was added tert-BuOLi (2.5 g, 31.2 mmol) at 5° C. in one portion. The solution was cooled to between 0 and 5° C. and trifluoroethyl trifluoromethanesulfonate (10.0 g, 43 mmol) was added in one portion. DMPU (7 mL) was added slowly over 15 min while maintaining the reaction temperature below 5° C. After the mixture was stirred at 0° C. for 3 h, additional tert-BuOLi (0.9 g, 11.2 mmol) was added. The mixture was aged for an additional 90 min. The mixture was quenched with 0.2 N HCl (70 ml), followed by addition of heptane (80 ml). The organic layer was separated and aqueous layer extracted with heptane (30 ml). The combined organic layers were washed with 15% aqueous citric acid (50 mL) and 5% aqueous NaHCO3 (50 mL). The solution was concentrated under vacuum at 40° C. and the resulting oil was dissolved in iPAc (30 mL). The solution was used directly in the next step without further purification. The HPLC analysis indicated that the solution contained 22 (9.8 g, 92% as cis and trans mixture in a ratio of 6.5 to 1) along with 4% of starting material 21 and 8% of a N,N′-alkylated compound. Analytically pure 22 (cis isomer) was isolated by chromatography on silica gel with ethyl acetate and heptane as an eluant. 1H NMR (CDCl3, 500 MHz): δ 7.15 (m, 1H), 6.85 (m, 1H), 5.45 (broad, s, 1H), 4.90 (m, H), 4.20 (m, 1H), 3.92 (m, 2H), 3.28 (m, 1H), 2.70 (m, 2H), 1.48 (s, 9H), 1.20 (d, J=5.9 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 170.2, 156.9 (ddd, J=245, 6.3, 2.7 Hz), 156.0, 149.6 (ddd, J=251, 14.8, 8.8 Hz), 147.6 (ddd, J=246, 13.9, 3.6 Hz), 124.5 (q, J=281 Hz), 117.6 (dd, J=19.2, 3.7 Hz), 116.4 (dd, J=19.1, 10.4 Hz), 111.4 (ddd, J=25.8, 6.4, 4.1 Hz), 56.6, 52.8, 45.3 (q, J=34.2 Hz), 35.2, 28.7, 28.3 (br t, J=4 Hz), 14.6; HRMS: m/z calcd for C19H22F6N2O3 (M+H): 441.1607. found 441.1617.

Aufarbeitung

  1. temperatureThe solution was cooled to between 0 and 5° C.
  2. temperaturewhile maintaining the reaction temperature below 5° C
  3. waitThe mixture was aged for an additional 90 min
  4. customThe mixture was quenched with 0.2 N HCl (70 ml)
  5. additionfollowed by addition of heptane (80 ml)
  6. customThe organic layer was separated
  7. extractionaqueous layer extracted with heptane (30 ml)
  8. washThe combined organic layers were washed with 15% aqueous citric acid (50 mL) and 5% aqueous NaHCO3 (50 mL)
  9. concentrationThe solution was concentrated under vacuum at 40° C.
  10. dissolutionthe resulting oil was dissolved in iPAc (30 mL)
  11. customThe solution was used directly in the next step without further purification
  12. customAnalytically pure 22 (cis isomer) was isolated by chromatography on silica gel with ethyl acetate and heptane as an eluant

Quellen und Nachweise

ORD-Eintrag
ord-a66140dc9fb3467ea4c3614c1c54439a
Quelldatensatz
uspto-grants-2015_11
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09174989B2

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