Asymmetric Oxidation Reactions Catalyzed By Chiral Iodine

The chemistry of hypervalent iodine has arisen to access unique reactivity,playing a significant role in modern organic synthesis.Given their versatile reactivity,low cost/toxicity,and environment-friendliness,hypervalent iodine reagents have been of intense interest and have been employed for developing mild text-book transformations during the past decades.In contrast,it was not until the last decade that chiral hypervalent iodine(?)catalysis arose as a privileged strategy for oxidative asymmetric synthesis.In this dissertation,efforts towards asymmetric oxidation catalyzed by in-situ generated chiral hypervalent iodine(?)catalyst from chiral aryl iodide has been summarized.Asymmetric dearomatization reaction is a premier transformation enabled by asymmetric hypervalentiodine(?)catalysis.Under mild oxidative conditions,we used a chiral aryl iodide as the pre-catalyst to drive the highly enantioselective dearomative C-C bond forming reaction of 1-naphthol derivatives,providing direct access to a series of spirooxindoles bearing all-carbon quaternary stereocenters.Moreover,through structural modification of current chiral aryl iodide pre-catalysts,we also achieved the asymmetric dearomatization of 2-naphthol derivatives to synthesize a library of multiple-functionalized enantiopure 2-oxindoles.Chiral ?-substituted ketones are found in numerous natural products and pharmaceuticals as the key structural unit.Asymmetric rearrangements consists one of the most efficient approaches to chiral ketones.By virtue of chiral hypervalent iodine(?)catalysis,we developed an asymmetric alkoxylation/oxidation rearrangement cascade reaction of diaryl allyl alcohols,accessing enantioenriched ?-arylated-?-alkoxylated ketones.