Triethylamine → HCID 68160224, Verbindung

HRID 537350Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 537350
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([C:21]#[N:22])[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CCN(CC)CC.[CH2:52]([O:54][C:55](=[O:58])[CH:56]=[CH2:57])[CH3:53]>CC([O-])=O.CC([O-])=O.[Pd+2].CC#N>[C:21]([C:8]1([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2/[CH:57]=[CH:56]/[C:55]([O:54][CH2:52][CH3:53])=[O:58])[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]1)#[N:22]

Komponenten

7

Edukt 4

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 49760259tert-Butyl 4-(2-bromophenyl)-4-cyanopiperidine-1-carboxylate

Produkt 1

HCID 68160224HCID 68160224, VerbindungAusbeute 96 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 6342AcetonitrileLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

Tert-butyl 4-(2-bromophenyl)-4-cyanopiperidine-1-carboxylate (20, 100 mg, 0.28 mmol) and Pd(OAc)2 (7.0 mg, 0.030 mmol) were added to a vial, followed by tri(o-tolyl)phosphine (14 mg, 0.047 mmol). The reaction vial was purged with Ar (3×). Dry CH3CN (1.4 mL) and Et3N (103 μL, 0.74 mmol) were added, followed by ethylacrylate (36 μL, 0.33 mmol). The reaction mixture was heated at 85° C. overnight. The reaction was concentrated. Et2O (2 mL) was added to the mixture and was then filtered through Celite. The crude residue was purified by silica gel chromatography (gradient, 10% to 20% EtOAc/hexanes) to yield (E)-tert-butyl 4-cyano-4-(2-(3-ethoxy-3-oxoprop-1-enyl)phenyl)piperidine-1-carboxylate as a pale yellow oil (21, 102 mg, 96% yield). 1H NMR (400 MHz, CDCl3): δ 8.51 (d, 1H), 7.58 (dd, 1H), 7.41 (td, 1H), 7.38-7.34 (m, 1H), 6.31 (d, 1H), 4.29 (q, 1H), 3.29 (bt, 2H), 2.35-2.31 (m, 2H), 1.90 (dt, 2H), 1.47 (s, 9H), 1.35 (t, 3H).

Aufarbeitung

  1. customThe reaction
  2. customvial was purged with Ar (3×)
  3. concentrationThe reaction was concentrated
  4. additionEt2O (2 mL) was added to the mixture
  5. filtrationwas then filtered through Celite
  6. customThe crude residue was purified by silica gel chromatography (gradient, 10% to 20% EtOAc/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-3e33360a79a447a293d4b8e230160e28
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08859776B2

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