Sodium bis(trimethylsilyl)amide → 3-Methyl-4-(oxetan-3-YL)benzonitrile

HRID 72961

Reaktionsgleichung

Reaktionsgleichung von HRID 72961
[C:1]([C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[C:5]([CH3:12])[CH:4]=1)#[N:2].N[C@H]1CC[CH2:17][CH2:16][C@@H:15]1[OH:20].C[Si]([N-][Si](C)(C)C)(C)C.[Na+].IC1COC1>C(O)(C)C.C(O)C.[Ni](I)I>[CH3:12][C:5]1[CH:4]=[C:3]([CH:8]=[CH:7][C:6]=1[CH:16]1[CH2:15][O:20][CH2:17]1)[C:1]#[N:2]

Komponenten

8

Edukt 4

HCID 2724254Sodium bis(trimethylsilyl)amideHCID 7057408(1S,2S)-2-aminocyclohexanolHCID 133566863-IodooxetaneHCID 16218401(4-Cyano-2-methyl-phenyl)boronic acid

Produkt 1

HCID 681533093-Methyl-4-(oxetan-3-YL)benzonitrileAusbeute 1.084,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 26038Nickel(II) iodideKatalysatorHCID 702EthanolLösungsmittelHCID 3776IsopropanolLösungsmittel2×

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

To (4-cyano-2-methyl-phenyl)boronic acid (1.75 g, 10.90 mmol), nickel iodide (0.10 g, 0.33 mmol), (1S,2S)-2-aminocyclohexan-1-ol (0.05 g, 0.33 mmol) and NaHMDS (2.01 g, 10.90 mmol) in isopropanol (10 mL) under an atmosphere of nitrogen was added 3-iodooxetane (1.00 g, 5.40 mmol) in isopropanol (1 mL) via cannula. The reaction mixture was heated at 90° C. for 2 hours, then cooled, diluted with ethanol (20 mL) and filtered over Celite®. The filtrate was concentrated in vacuo, then the residue was purified by silica gel column chromatography using 0-60% EtOAc/hexane as eluant to give 3-methyl-4-(oxetan-3-yl)benzonitrile (0.62 g, 65%) as a white solid. ESI-MS m/z calc. 173.1. Found 174.3 (M+1)+; Retention time: 1.09 minutes (3 min run).

Aufarbeitung

  1. temperaturecooled
  2. filtrationfiltered over Celite®
  3. concentrationThe filtrate was concentrated in vacuo
  4. customthe residue was purified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-6674a7d3f6bf41d68a7003dfc5ff049f
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08828996B2

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