Enantioselective Diels-Alder Reaction Using Chiral Mg Complexes Derived from Chiral 2-[2-[(Alkyl- or 2-[2-[(Arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazoline.
Magnesium complexes derived from (R)-2-[2-[(alkyl- or (R)-2-[2-[(arylsulfonyl)amino]phenyl]-4-phenyl-1,3-oxazolines and methylmagnesium iodide were found to be efficient Lewis acid catalysts for the Diels-Alder reaction of 3-alkenoyl-1,3-oxazolidin-2-one with cyclopentadiene. Chiral ligands were easily prepared from readily available D-phenylglycinol in good yields. The reaction of 3-acryloyl-1,3-oxazolidin-2-one with cyclopentadiene catalyzed by a stoichiometric amount of the Lewis acid gave exclusively the endo-cycloaddition product in up to 92% ee. The sulfonamide group on the chiral ligand strongly influenced the enantiofacial selectivity: the use of a toluene-, benzene-, 1- or 2-naphthalene-, or methanesulfonamide group in the chiral ligand gave the endo-(2R)-cycloaddition product, while a trifluoromethanesulfonamide group predominantly gave its enantiomer, the endo-(2S)-cycloaddition product, in 65% ee. The scope and limitations of the catalytic effect of chiral Mg(II) complexes on the enantioselectivity of the Diels-Alder reaction were investigated. The reaction mechanism of the Mg(II)-catalyzed reaction is also discussed on the basis of the experimental results.
Ichiyanagi
Tsuyoshi
T
Department of Chemistry for Materials, Mie University, Tsu, Mie 514, Japan.
Shimizu
Makoto
M
Fujisawa
Tamotsu
T