Tributylvinyltin → (S)-ethyl 2-tert-butoxy-2-(3-methyl-1-(trifluoromethylsulfonyloxy)-6-vinylnaphthalen-2-yl)acetate

HRID 926179Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 926179
[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].[CH:32]([Sn](CCCC)(CCCC)CCCC)=[CH2:33].C([O-])(O)=O.[Na+]>CN(C=O)C.CC(C1C=C(C(C)C)C(C2C(P(C3CCCCC3)C3CCCCC3)=C(OC)C=CC=2OC)=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]([CH:32]=[CH2:33])[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 81998TributylvinyltinHCID 516892Sodium BicarbonateHCID 89681783(S)-ethyl 2-tert-butoxy-2-(6-chloro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

Produkt 1

HCID 89733247(S)-ethyl 2-tert-butoxy-2-(3-methyl-1-(trifluoromethylsulfonyloxy)-6-vinylnaphthalen-2-yl)acetate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 25112666BrettPhos PalladacycleKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

A solution of (S)-ethyl 2-tert-butoxy-2-(6-chloro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate (1.0 g, 2.1 mmol) in DMF (10 mL) at room temperature is treated with BrettPhos precatalyst (Strem, 0.23 g, 0.31 mmol), vinyl tributyltin (0.68 mL, 2.3 mmol) and solid NaHCO3 (0.026 g, 0.31 mmol). The reaction mixture is sealed and sparged with Ar for 10 minutes prior to heating at 120° C. for 90 minutes. The reaction mixture is allowed to cool to room temperature, loaded directly onto silica gel and purified via Yamazen column chromatography to afford (S)-ethyl 2-tert-butoxy-2-(3-methyl-1-(trifluoromethylsulfonyloxy)-6-vinylnaphthalen-2-yl)acetate. 1H-NMR: 400 MHz, (CDCl3) δ: 8.00 (d, J=8.8 Hz, 1H); 7.72 (d, J=8.8 Hz, 1H); 7.70 (s, 1H); 7.64 (s, 1H); 6.87 (dd, J=17.2, 11.2 Hz, 1H); 5.92 (d, J=17.2 Hz, 1H); 5.41 (d, J=11.2 Hz, 1H); 4.27-4.08 (m, 2H); 2.55 (s, 3H); 1.22 (s, 9H); 1.18 (t, J=7.2 Hz, 3H).

Aufarbeitung

  1. customThe reaction mixture is sealed
  2. customsparged with Ar for 10 minutes
  3. temperatureto cool to room temperature
  4. custompurified via Yamazen column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-302c119db55646caa2fc8c3d16af3391
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09284323B2

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