Tetrabutylammonium Fluoride → 1289023-89-7

HRID 1879360Notes

Reaction equation

HRID 1879360 reaction equation
[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[CH:9]1[CH2:19][CH2:18][C@@H:17]([O:20][Si](C(C)C)(C(C)C)C(C)C)[C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:11]2[C:10]1=[O:31].CCCC[N+](CCCC)(CCCC)CCCC.[F-].C(OCC)(=O)C.CCCCCC>O1CCCC1>[F:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C@@H:9]1[CH2:19][CH2:18][C@@H:17]([OH:20])[C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:11]2[C:10]1=[O:31]

Participants

5

Reactant 3

HCID 2724141Tetrabutylammonium FluorideHCID 21226206Ethyl acetate hexaneHCID 66811345HCID 66811345, compound

Product 1

HCID 584679831289023-89-7Yield 79%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-15 °C

Procedure

In a 250 mL round-bottom flask was dissolved (9R)-6-(2,3-difluorophenyl)-9-(triisopropylsilyloxy)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-one (0.218 g, 0.49 mmol) in tetrahydrofuran (5 mL) to give a colorless solution. After cooling to −15° C. (ice-methanol bath) under nitrogen, TBAF (0.490 mL, 0.490 mmol) was added, and the resulting bright yellow solution was stirred at −15° C. for 1 h (12:00 pm). It was quenched with sodium bicarbonate solution and diluted with ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers was washed with brine, dried and concentrated to give a tan oil. FCC (25 g silica gel column) up to 100% ethyl acetate/hexane afforded the desired product (112 mg, 62%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.53 (dd, J=4.91, 1.64 Hz, 1H) 7.85 (dd, J=7.68, 1.64 Hz, 1H) 7.34 (dd, J=7.68, 4.91 Hz, 1H) 7.00-7.16 (m, 3H) 5.32 (s, 1H) 4.94-5.04 (m, 1H) 4.48 (dd, J=11.83, 3.02 Hz, 1H) 2.14-2.48 (m, 4H); 19F NMR (376 MHz, CHLOROFORM-d) δ ppm −138.24-−138.07 (m, 1F) −140.70-−140.50 (m, 1F).

Workup

  1. customto give a colorless solution
  2. customIt was quenched with sodium bicarbonate solution
  3. additiondiluted with ethyl acetate
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with ethyl acetate
  6. washThe combined organic layers was washed with brine
  7. customdried
  8. concentrationconcentrated
  9. customto give a tan oil

Sources & evidence

ORD record
ord-e0e98f995d1b42f490b80280da764d62
Source dataset
uspto-grants-2012_11
Patent number
US08314117B2

Reaction notes

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