Ytterbium triflate → HCID 66823396, compound

HRID 1193236Notes

Reaction equation

HRID 1193236 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([CH:14]3[CH2:16][CH2:15]3)=[C:10]([CH:17]3[C:19]4([C:23](=[O:24])[C:22]([CH3:26])([CH3:25])[O:21][C:20]4([CH3:28])[CH3:27])[O:18]3)[CH:9]=2)=[C:4]([F:29])[CH:3]=1.[O-]S(C(F)(F)F)(=O)=O.[Yb+3].[O-]S(C(F)(F)F)(=O)=O.[O-]S(C(F)(F)F)(=O)=O.Cl([O-])(=O)(=O)=O.[Li+]>C(OCC)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([CH:14]3[CH2:15][CH2:16]3)=[C:10]([CH:17]3[C:19](=[O:18])[C:20]([CH3:27])([CH3:28])[O:21][C:22]([CH3:25])([CH3:26])[C:23]3=[O:24])[CH:9]=2)=[C:4]([F:29])[CH:3]=1

Participants

5

Reactant 3

HCID 2733225Ytterbium triflate3×HCID 23665649Lithium perchlorate2×HCID 86663670HCID 86663670, compound

Product 1

HCID 66823396HCID 66823396, compoundYield 26.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a mixture of 2-(4′-chloro-4-cyclopropyl-2′-fluorobiphenyl-3-yl)-4,4,6,6-tetramethyl-1,5-dioxaspiro[2.4]heptan-7-one (18.20 g, 0.044 mol) and ytterbium triflate (2.40 g, 4.40 mmol) is added a solution of 5M lithium perchlorate (prepared from 46 ml diethyl ether and 24.40 g lithium perchlorate). The resulting suspension is stirred at room temperature for 3 days, then is diluted with diethyl ether (85 ml) and additional ytterbium triflate (7.80 g, 0.014 mol) is added. After stirring at room temperature for a further 3 days additional ytterbium triflate (13.63 g, 0.025 mol) is added, and the reaction mixture is stirred for 11 days. Finally, extra lithium perchlorate (24.40 g, 0.23 mol) is added in one portion, and the mixture is heated at 27° C. (internal temperature) for 1 day. The reaction mixture is partitioned between diethyl ether and distilled water, the two phases separated, and the aqueous phase is extracted with diethyl ether (×2). The organic fractions are combined, washed with brine then dried over magnesium sulphate. The suspension is filtered and the filtrate concentrated in vacuo. The crude material purified by flash column chromatography (10% ethyl acetate in hexanes as eluant) to afford an oil which is triturated with hexanes to afford 4-(4′-chloro-4-cyclopropyl-2′-fluorobiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dione (4.78 g) as a white solid.

Workup

  1. additionis added
  2. additionis added
  3. stirringthe reaction mixture is stirred for 11 days
  4. temperaturethe mixture is heated at 27° C. (internal temperature) for 1 day
  5. customThe reaction mixture is partitioned between diethyl ether
  6. distillationdistilled water
  7. customthe two phases separated
  8. extractionthe aqueous phase is extracted with diethyl ether (×2)
  9. washwashed with brine
  10. dry with materialthen dried over magnesium sulphate
  11. filtrationThe suspension is filtered
  12. concentrationthe filtrate concentrated in vacuo
  13. customThe crude material purified by flash column chromatography (10% ethyl acetate in hexanes as eluant)
  14. customto afford an oil which
  15. customis triturated with hexanes

Sources & evidence

ORD record
ord-754f147fec24421aaf17e87c80344c32
Source dataset
uspto-grants-2014_03
Patent number
US08680299B2

Reaction notes

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