Trimethylsilyldiazomethane → Methyl 2-(4-bromo-1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-(tert-butyldimethylsilyloxy)acetate

HRID 514143Notes

Reaction equation

HRID 514143 reaction equation
[Br:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=2)=[C:4]([CH:19]([O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])[C:20]([OH:22])=[O:21])[C:3]=1[CH3:31].[Si](C=[N+]=[N-])(C)(C)[CH3:33].BrC1C2C(=CC=CC=2)C(C2C=CC(Cl)=CC=2)=C(C(O[Si](C(C)(C)C)(C)C)C=O)C=1C>C(Cl)Cl.CO>[Br:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([C:12]2[CH:13]=[CH:14][C:15]([Cl:18])=[CH:16][CH:17]=2)=[C:4]([CH:19]([O:23][Si:24]([C:27]([CH3:28])([CH3:30])[CH3:29])([CH3:25])[CH3:26])[C:20]([O:22][CH3:33])=[O:21])[C:3]=1[CH3:31]

Participants

5

Reactant 3

HCID 167693TrimethylsilyldiazomethaneHCID 671261952-(4-Bromo-1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-(tert-butyldimethylsilyloxy)acetic acidHCID 866915662-(4-Bromo-1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-(tert-butyldimethylsilyloxy)acetaldehyde

Product 1

HCID 67126260Methyl 2-(4-bromo-1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-(tert-butyldimethylsilyloxy)acetateYield 78%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent

Conditions

Temperature
23 °C

Procedure

Crude 2-(4-bromo-1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-(tert-butyldimethylsilyloxy)acetic acid 0.740 g, 1.4 mmol)was dissolved in 20 mL DCM-MeOH (50-50, v/v) and combined with TMS-diazomethane solution (7.0 mL, 2.0 M in hexanes) and allowed to stir 6 hrs at 23° C. The reaction was cooled on ice and quenched by the slow addition of TFA (500 μL) which simultaneously removed the yellow color from the reaction mixture. Mixture was diluted with DCM and washed with brine, then dried and concentrated in vacuo. Purification by silica gel chromatography with EtOAc in hexanes provided purified material (537.8 mg, 78% yield) from the 2-(4-bromo-1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-(tert-butyldimethylsilyloxy)acetaldehyde. 1H-NMR: (400 MHz, MeOH-d4): δ 8.39 (d, J=8.0 Hz, 1H); 7.58-7.54 (m, 1H); 7.50-7.47 (m, 2H); 7.37-7.33 (m, 2H); 7.27-7.21 (m, 2H); 5.31 (s, 1H); 3.69 (s, 3H); 2.67 (s, 3H); 0.83 (s, 9H); −0.04 (s, 3H); −0.27 (s, 3H).

Workup

  1. temperatureThe reaction was cooled on ice
  2. customquenched by the slow addition of TFA (500 μL) which
  3. customsimultaneously removed the yellow color from the reaction mixture
  4. additionMixture was diluted with DCM
  5. washwashed with brine
  6. customdried
  7. concentrationconcentrated in vacuo
  8. customPurification by silica gel chromatography with EtOAc in hexanes
  9. customprovided

Sources & evidence

ORD record
ord-0d0c0001155f4542844294a693736bed
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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