Highly Diastereoselective Intermolecular β-Addition of Alkyl Radicals to Chiral 2-(Arylsulfinyl)-2-cycloalkenones

Abstract

The diastereoselectivity of intermolecular β-addition of alkyl radicals to 2-(arylsulfinyl)-2-cycloalkenones depends largely upon the structure of the arylsulfinyl group. The reaction of 2-cyclopentenones or 2-cyclohexenones having a sterically bulky arylsulfinyl group such as (3,5-di-tert-butyl-4-methoxyphenyl)sulfinyl, (2,4,6-triisopropylphenyl)sulfinyl or (2,4,6-trimethylphenyl)sulfinyl group gives 3-alkyl-2-(arylsulfinyl)-1-cyclopentanones or 3-alkyl-2-(arylsulfinyl)-1-cyclohexanones in excellent yields and with high diastereoselectivity. Both the X-ray crystallographic analysis and the NOE experiment in the 1H NMR spectrum of (S)-2-[(2,4,6-triisopropylphenyl)sulfinyl]- and (S)-2-[(2,4,6-trimethylphenyl)sulfinyl]-2-cyclopentenone reveal an effective shielding of one of the olefin faces at the β-position by o-isopropyl and o-methyl groups. The addition of bidentate Lewis acids reverses the stereoselection through chelating the intermediates to give the addition products with high diastereoselectivity.