Dichloromethane → HCID 90123469, compound

HRID 633650Notes

Reaction equation

HRID 633650 reaction equation
C(Cl)Cl.[CH3:4][O:5][C:6]1[C:7]([CH2:19][C@@H:20]2[O:22][C@@:21]2([CH3:29])[CH2:23][CH2:24][CH:25]=[C:26]([CH3:28])[CH3:27])([CH2:14][CH:15]=[C:16]([CH3:18])[CH3:17])[C:8]([O:12][CH3:13])=[CH:9][CH2:10][CH:11]=1.C(C1C=C(C)C=C(C(C)(C)C)N=1)(C)(C)C.FC(F)(F)S(O[Si](C)(C)C)(=O)=O>CCOC(C)=O.CCCCCC>[CH3:4][O:5][C:6]1[C@@:7]2([CH2:14][CH:15]=[C:16]([CH3:18])[CH3:17])[CH2:19][CH:20]3[O:22][C@@:8]2([O:12][CH3:13])[C@H:9]([CH2:10][CH:11]=1)[C@:21]3([CH3:29])[CH2:23][CH2:24][CH:25]=[C:26]([CH3:27])[CH3:28]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 65367Trimethylsilyl triflateHCID 988982,6-Di-tert-butyl-4-methylpyridineHCID 86718441HCID 86718441, compound

Product 1

HCID 90123469HCID 90123469, compoundYield 90.6%

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

A DCM (100 mL) solution of 12 (1.88 g, 5.21 mmol, 1 equiv.) and 2,6-di-tert-butyl-4-methylpyridine (2.14 g, 10.4 mmol, 2 equiv.) was cooled to −78° C. in a 250-mL round-bottom flask, and trimethylsilyl trifluoromethanesulfonate (1.13 mL, 6.26 mmol, 1.2 equiv.) was slowly added. Immediately upon this addition, the solution turned bright yellow. After stirring at −78° C. for 45 min, the reaction was quenched with saturated aqueous NaHCO3 and allowed to warm to room temperature. The mixture was then extracted thrice with EtOAc. The organic extracts were combined, washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to a faintly yellow residue. Flash column chromatography (30 mL SiO2, 99:1 to 19:1 hexane:EtOAc) afforded 1.70 g (4.72 mmol, 90% yield) of 13 as a white, crystalline solid. 1H NMR (600 MHz; CDCl3): δ 5.34 (t, J=7.1 Hz, 1H), 5.03 (t, J=7.1 Hz, 1H), 4.52 (dd, J=5.5, 2.0 Hz, 1H), 3.74 (d, J=5.1 Hz, 1H), 3.48 (s, 3H), 3.46 (s, 3H), 2.36 (dd, J=14.7, 6.9 Hz, 1H), 2.22-2.17 (m, 2H), 2.03 (td, J=8.6, 6.4 Hz, 2H), 2.01-1.94 (m, 1H), 1.82 (d, J=12.4 Hz, 1H), 1.78 (dd, J=12.4, 5.1 Hz, 1H), 1.69 (s, 3H), 1.67 (s, 3H), 1.61 (s, 3H), 1.58 (s, 3H), 1.45 (td, J=13.0, 4.8 Hz, 1H), 1.22 (td, J=13.0, 4.6 Hz, 1H), 1.14 (s, 3H). 13C NMR (125 MHz; CDCl3): δ 158.5, 131.6, 131.2, 124.9, 123.6, 112.7, 90.6, 78.9, 54.6, 51.4, 46.5, 44.4, 42.0, 39.4, 33.6, 32.8, 28.2, 26.4, 25.9, 22.9, 20.1, 18.00, 17.85. HRMS-ESI (m/z): [M+H]+ calculated for C23H36O3, 361.2737. found, 361.2730.

Workup

  1. additionImmediately upon this addition
  2. customthe reaction was quenched with saturated aqueous NaHCO3
  3. temperatureto warm to room temperature
  4. extractionThe mixture was then extracted thrice with EtOAc
  5. washwashed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo to a faintly yellow residue

Sources & evidence

ORD record
ord-f8c2e70f83af46aab604b190915a3dce
Source dataset
uspto-grants-2016_04
Patent number
US09321713B2

Reaction notes

Loading…