Potassium Carbonate → Ethyl 1-((6-((4-tert-butylcyclohexylidene)methyl)naphthalen-2-yl)methyl)piperidine-4-carboxylate

HRID 525484

Reaktionsgleichung

Reaktionsgleichung von HRID 525484
FC(F)(F)S(O[C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][CH:16]=1)[CH:13]=[C:12]([CH2:17][N:18]1[CH2:23][CH2:22][CH:21]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:20][CH2:19]1)[CH:11]=[CH:10]2)(=O)=O.[C:31]([CH:35]1[CH2:40][CH2:39][C:38](=[CH2:41])[CH2:37][CH2:36]1)([CH3:34])([CH3:33])[CH3:32].C([O-])([O-])=O.[K+].[K+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>CC([O-])=O.CC([O-])=O.[Pd+2].CN1C(=O)CCC1>[C:31]([CH:35]1[CH2:36][CH2:37][C:38](=[CH:41][C:7]2[CH:8]=[C:9]3[C:14](=[CH:15][CH:16]=2)[CH:13]=[C:12]([CH2:17][N:18]2[CH2:19][CH2:20][CH:21]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:22][CH2:23]2)[CH:11]=[CH:10]3)[CH2:39][CH2:40]1)([CH3:34])([CH3:33])[CH3:32]

Komponenten

7

Edukt 4

HCID 11430Potassium CarbonateHCID 139425Cyclohexane, 1-(1,1-dimethylethyl)-4-methylene-HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 88920371Ethyl 1-((6-(trifluoromethylsulfonyloxy)naphthalen-2-yl)methyl)piperidine-4-carboxylate

Produkt 1

HCID 68279484Ethyl 1-((6-((4-tert-butylcyclohexylidene)methyl)naphthalen-2-yl)methyl)piperidine-4-carboxylateAusbeute 35,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 13387N-methyl-2-pyrrolidoneLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

Into a sealed tube were added ethyl 1-((6-(((trifluoromethyl)sulfonyl)oxy)naphthalen-2-yl)methyl)piperidine-4-carboxylate (500 mg, 1.12 mmol), 1-(tert-butyl)-4-methylenecyclohexane (340 mg, 2.24 mmol, 2 eq), K2CO3 (309 mg, 2.24 mmol, 2 eq), Xantphos (130 mg, 0.22 mmol, 0.2 eq), Pd(OAc)2 (25 mg, 0.11 mmol, 0.1 eq) and NMP (2 mL). The mixture was flushed with N2 for 5 min. Then the reaction was stirred at 120° C. for 12 h. The reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (5 mL×3). The organic solvent was removed in vacuum and the residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=2:1) to give ethyl 1-((6-((4-(tert-butyl)cyclohexylidene)methyl)naphthalen-2-yl)methyl)piperidine-4-carboxylate (180 mg, yield: 35%) as a yellow solid. ESI-MS (M+1)+: 448.3. 1H NMR (400 MHz, CDCl3) δ: 7.76-7.73 (m, 2H), 7.68 (s, 1H), 7.61 (s, 1H), 7.46 (d, J=8.0 Hz, 1H), 7.34 (d, J=8.8 Hz, 1H), 6.34 (s, 1H), 4.13 (q, J=8.8 Hz, 2H), 3.64 (s, 2H), 2.92-2.89 (m, 2H), 2.30-2.25 (m, 2H), 2.08-2.05 (m, 2H), 1.94-1.77 (m, 8H), 1.60 (br, 2H), 1.26-1.23 (m, 5H), 0.87 (s, 9H).

Aufarbeitung

  1. customThe mixture was flushed with N2 for 5 min
  2. additionThe reaction mixture was diluted with ethyl acetate (20 mL)
  3. washwashed with water (5 mL×3)
  4. customThe organic solvent was removed in vacuum
  5. customthe residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=2:1)

Quellen und Nachweise

ORD-Eintrag
ord-0d07032fc685440aaf38913217a0c154
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09340527B2

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