Abstract
Chiral cationic palladium(II) 2-(phosphinophenyl)pyridine (1a ) complex was found to be an effective
catalyst for asymmetric Baeyer-Villiger oxidation of prochiral
cyclobutanones. For example, good and excellent enantioselectivities
(80% and >99% ees) were achieved in the
reactions of 3-phenylcyclobutanone and a tricyclic cyclobutanone,
respectively.
Key words
asymmetric Baeyer-Villiger oxidation - asymmetric catalysis - palladium - chiral P-N ligand
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11
Typical experimental
procedure
To a solution of bis(benzonitrile)palladium(II)
chloride (1.9 mg, 5.0 mol) in THF (0.4 mL) was added ligand 1a (2.3 mg, 5.5 mol) under nitrogen and
stirred at room temperature for 1 h. Silver hexafluoroantimonate
(3.4 mg, 10 mol) was placed another flask under nitrogen and to
this flask was added the above palladium(II)-1a dichloride
solution. After being stirred for 1 h at room temperature, the mixture
was filtered through a pad of Celite under nitrogen. To the filtrate was
added 3-phenylcyclobutanone (15.2 mg, 0.1 mmol) and then cooled
to -60 °C. To the cooled solution was added UHP
(12.2 mg, 0.13 mmol) and the mixture was further stirred at the
temperature for 214 h. The mixture was concentrated and the residue
was chromatographed on silica gel (hexane-EtOAc, 9:1) to
give dihydro-4-phenylfuran-2(3H )-one
(14.8 mg, 91%). The enantiomeric excess of the product
was determined to be 80% ee by HPLC analysis using chiral
stationary phase column (Daicel Chiralpak AD-H; hexane-i -PrOH, 95:5).
