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

HRID 926179Notes

Reaction equation

HRID 926179 reaction equation
[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]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 516892Sodium BicarbonateHCID 89681783(S)-ethyl 2-tert-butoxy-2-(6-chloro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

Product 1

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

Reagents, catalysts & solvents 2

HCID 25112666BrettPhos PalladacycleCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-302c119db55646caa2fc8c3d16af3391
Source dataset
uspto-grants-2016_03
Patent number
US09284323B2

Reaction notes

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