Dimethylformamide → (S)-ethyl 2-tert-butoxy-2-(6-cyano-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

HRID 926144Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 926144
[C:1]([O:5][C@@H:6]([C:12]1[C:21]([CH3:22])=[CH:20][C:19]2[C:14](=[CH:15][CH:16]=[C:17](Cl)[CH:18]=2)[C:13]=1[O:24][S:25]([C:28]([F:31])([F:30])[F:29])(=[O:27])=[O:26])[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:4])([CH3:3])[CH3:2].C(=O)(O)[O-].[Na+].[CH3:37][N:38](C=O)C>[C-]#N.[Zn+2].[C-]#N.CC(C1C=C(C(C)C)C(C2C(P(C3CCCCC3)C3CCCCC3)=CC=CC=2)=C(C(C)C)C=1)C.C1C=[C-]C(CCN)=CC=1.Cl[Pd+]>[C:1]([O:5][C@@H:6]([C:12]1[C:21]([CH3:22])=[CH:20][C:19]2[C:14](=[CH:15][CH:16]=[C:17]([C:37]#[N:38])[CH:18]=2)[C:13]=1[O:24][S:25]([C:28]([F:31])([F:30])[F:29])(=[O:27])=[O:26])[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:4])([CH3:3])[CH3:2]

Komponenten

6

Edukt 3

HCID 6228DimethylformamideHCID 516892Sodium BicarbonateHCID 89681783(S)-ethyl 2-tert-butoxy-2-(6-chloro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

Produkt 1

HCID 131735014(S)-ethyl 2-tert-butoxy-2-(6-cyano-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 54751079XPhos PalladacycleKatalysator

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

A mixture of (S)-ethyl 2-tert-butoxy-2-(6-chloro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate (0.546 g, 1.13 mmol), zinc(II) cyanide (0.080 g, 0.678 mmol), XPhos Palladacycle (Strem, 0.083 g, 0.113 mmol) and sodium bicarbonate (0.009 g, 0.113 mmol) in DMF (3.0 mL) was sparged with nitrogen for 5 minutes. The reaction mixture was heated in microwave at 110° C. for 1 hour. The reaction mixture was diluted with ethyl acetate and washed with 5% lithium chloride solution (2×), brine and dried (MgSO4) and filtered. Concentration and purification by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes) gave the title compound. NMR (400 MHz, CDCl3) δ 8.19 (s, H), 8.13 (d, J=8.8 Hz, H), 7.74 (s, H), 7.71 (d, J=8.8 Hz, H), 5.73 (s, H), 4.27-4.09 (m, 2H), 2.59 (s, 3H), 1.21 (s, 9H), 1.17 (t, J=7.1 Hz, 2H).

Aufarbeitung

  1. customwas sparged with nitrogen for 5 minutes
  2. additionThe reaction mixture was diluted with ethyl acetate
  3. washwashed with 5% lithium chloride solution (2×), brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationConcentration and purification by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-4ffe05183e484b268034dad5f785f50b
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09284323B2

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