Dimethylformamide → (2RS,4SR)-4-(Benzyloxy)-2-fluoro-cyclohexan-1-one

HRID 271375Notes

Reaction equation

HRID 271375 reaction equation
CN(C)C=O.[CH2:6]([O:13][CH:14]1[CH2:19][CH2:18][C:17]([O:20][Si](C(C)(C)C)(C)C)=[CH:16][CH2:15]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[B-](F)(F)(F)[F:29].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1.C(=O)(O)[O-].[Na+]>C(OCC)(=O)C.CCCCCC>[CH2:6]([O:13][CH:14]1[CH2:19][CH2:18][C:17](=[O:20])[CH:16]([F:29])[CH2:15]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 516892Sodium BicarbonateHCID 2724933SelectfluorHCID 68669646{[4-(Benzyloxy)cyclohex-1-en-1-yl]oxy}(tert-butyl)dimethylsilane

Product 1

HCID 59543141(2RS,4SR)-4-(Benzyloxy)-2-fluoro-cyclohexan-1-oneYield 62%

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A N,N-dimethylformamide (150 mL) solution of {[4-(Benzyloxy)cyclohex-1-en-1-yl]oxy}(tert-butyl)dimethylsilane (23.2 g, 73.0 mmol) was cooled in an ice bath under nitrogen and to this was added Selectfluor™ (51.6 g, 146 mmol) in several portions. After 1 h the contents of the reaction flask were poured into 5% sodium bicarbonate. The resulting mixture was extracted with ethyl acetate (4×) and the combined organic extracts were washed successively with water and brine, dried with anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Flash column chromatography (hexane:ethyl acetate, 80:20) gave 4-(Benzyloxy)-2-fluorocyclohexanone as a pale oil (10.0 g, 62% yield): 1H NMR (CDCl3) δ 7.39-7.30 (m, 5H), 5.36-5.19 (m, 1H), 4.61 (s, 2H), 4.02 (m, 1H), 2.81-2.73 (m, 2H), 2.45-2.41 (m, 1H), 2.36-2.30 (m, 1H), 2.05-1.88 (m, 1H), 1.85-1.77 (m, 1H).

Workup

  1. extractionThe resulting mixture was extracted with ethyl acetate (4×)
  2. washthe combined organic extracts were washed successively with water and brine
  3. dry with materialdried with anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b3fcde0cdd7b467db7d44548ad55ca67
Source dataset
uspto-grants-2008_11
Patent number
US07452893B2

Reaction notes

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