Photochemical Deracemization of Chiral Sulfoxides Catalyzed by a Hydrogen-Bonding Xanthone Sensitizer

In memory of Dieter Enders

Abstract

Several chiral sulfoxides with a lactam hydrogen-bonding site were prepared and their photochemical behavior was studied in the presence of xanthone and thioxanthone sensitizers. While acyclic sulfoxides showed only decomposition, chiral benzothiazinone-1-oxides with a stereogenic sulfur atom underwent a stereomutation upon irradiation at λ = 366 nm in the presence of catalytic quantities of a xanthone sensitizer. A chiral xanthone with a 1,5,7-trimethyl-3-azabicyclo-[3.3.1]nonan-2-one backbone was employed in catalytic quantities (5 mol%) to achieve a deracemization reaction of racemic benzothiazinone-1-oxides in acetonitrile solution. Five substrates could be successfully deracemized in good yields and with up to 55% ee.

Key words

deracemization - enantioselective synthesis - homogeneous catalysis - photochemistry - sensitization - sulfoxides

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