HCID 178488804, compound → HCID 178488805, compound

HRID 1489200Notes

Reaction equation

HRID 1489200 reaction equation
[C:1]([C:5]1[C:10]([O:11][SiH:12]([CH3:14])[CH3:13])=[C:9]([Br:15])[C:8]([O:16][CH3:17])=[CH:7][C:6]=1[CH2:18][CH:19]1[C:24](=[O:25])[CH:23]=[CH:22][CH2:21][C:20]1([CH3:27])[CH3:26])([CH3:4])([CH3:3])[CH3:2]>C(OCC)(=O)C.[Pd]>[C:1]([C:5]1[C:10]([O:11][SiH:12]([CH3:13])[CH3:14])=[C:9]([Br:15])[C:8]([O:16][CH3:17])=[CH:7][C:6]=1[CH2:18][CH:19]1[C:20]([CH3:27])([CH3:26])[CH2:21][CH2:22][CH2:23][C:24]1=[O:25])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 1

HCID 178488804HCID 178488804, compound

Product 1

HCID 178488805HCID 178488805, compoundYield 75.4%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a flame-dried round-bottomed flask containing 6-[2'-(tert-butyl)dimethylsilyloxy-4'-bromo-5'-methoxyphenyl]methyl-5,5-dimethylcyclohex-2-en-1-one (13) (0.154 g, 0.454 mmol) in 22 mL ethyl acetate (which had been pre-dried over K2CO3) at room temperature was added 20 mg 5% palladium on carbon, and after flushing / evacuating the vessel 3 times with nitrogen, a hydrogen atmosphere was introduced and maintained by use of a balloon. After 24 h, the flask was again flushed several times with nitrogen, and the contents of the flask were filtered, rinsing with an additional 100 mL ethyl acetate. Rotary evaporation of the solvent afforded 0.156 g (quantitative) of the saturated benzylic ketone as a colorless, viscous oil (Rf 0.67, 2:1 hexanes/ethyl acetate). 1H NMR (400 MHz, CDCl3) δ0.22 and 0.25 [2s, 2×3H, Si(CH3)2 ], 0.87 and 1.12 (2s, 2×3H, geminal-CH3 's), 1.01 [s, 9H, SiC(CH3)3 ], 3.71 (s, 3H, OCH3), 6.79 (s, 1H, 6'-H), 6.91 ppm (s, 1H, 3'-H).

Workup

  1. customafter flushing / evacuating the vessel 3 times with nitrogen
  2. additiona hydrogen atmosphere was introduced
  3. temperaturemaintained by use of a balloon
  4. filtrationthe contents of the flask were filtered
  5. washrinsing with an additional 100 mL ethyl acetate
  6. customRotary evaporation of the solvent

Sources & evidence

ORD record
ord-a2b7e3952f094e9ea84692432992d3f6
Source dataset
uspto-grants-1997_10
Patent number
US05677336

Reaction notes

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