Dimethyl Sulfoxide → 3-methyl-6-(methylsulfonyl)-3,4-dihydronaphthalen-1(2H)-one
Reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8](=[O:12])[CH2:7][CH:6]([CH3:13])[CH2:5]2.[Na].C(=O)([O-])[O-].[Cs+].[Cs+].N1CCC[C@H]1C(O)=[O:24].C[S:30]([CH3:32])=[O:31]>[Cu]I>[CH3:13][CH:6]1[CH2:5][C:4]2[C:9](=[CH:10][CH:11]=[C:2]([S:30]([CH3:32])(=[O:24])=[O:31])[CH:3]=2)[C:8](=[O:12])[CH2:7]1Participants
Reactant 5
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 100 °C
Procedure
A mixture of 6-bromo-3-methyl-3,4-dihydronaphthalen-1(2H)-one (10 g, 41.8 mmol) methanesulfinic acid, sodium salt (16.7 g, 163.1 mmol), copper(I) iodide (3.18 g, 16.7 mmol), cesium carbonate (6.81 g, 20.9 mmol) and L-proline (3.85 g, 33.4 mmol) in DMSO (200 mL) was heated at 100° C., protected from light. After 3.5 hours, copper(I) iodide (1.59 g) and L-proline (1.9 g) were added and the reaction continued for 5 hours, and then stirred overnight at room temperature. The mixture was diluted with ice/water (200 mL) and extracted with ethyl ether (3×), ethyl acetate (3×). The combined organic layer was washed with brine, dried (MgSO4), filtered, and purified by flash column chromatography (silica gel, 30 to 60% ethyl acetate/hexanes) to give the desired product. 1H NMR (400 MHz, CDCl3) δ 8.20 (d, J=8.1 Hz, 1H), 7.87 (s, 1H), 7.86 (d, J=7.7 Hz, 1H), 3.10-3.00 (m, 1H), 3.08 (s, 3H), 2.86-2.71 (m, 2H), 2.48-2.31 (m, 2H), 1.19 (d, J=6.0 Hz, 3H).
Workup
- waitthe reaction continued for 5 hours
- extractionextracted with ethyl ether (3×), ethyl acetate (3×)
- washThe combined organic layer was washed with brine
- dry with materialdried (MgSO4)
- filtrationfiltered
- custompurified by flash column chromatography (silica gel, 30 to 60% ethyl acetate/hexanes)
Sources & evidence
- ORD record
- ord-9271670f37d246fc98bbf857813e55b2
- Source dataset
- uspto-grants-2016_03
- Patent number
- US09284323B2
Reaction notes
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