Chiral aryliodine(III)r eagents have provided an advancedc oncept for enantioselective synthesis and catalysis.W ith the advent of chiral iodine(I/III) catalysis,m anyd ifferent structures have been explored in the area. Thec urrently most prominent catalyst design is based on ar esorcinol core and the attachment of two lactic side chainsb earing ester or amide groups.T his enables ap rivileged modular catalyst synthesis,i nw hich fine-tuning with respect to the specificr eaction requirement is straightforward. Thep resent overview summarizes the structural variation and optimization of such chiral aryliodine catalysts andd iscusses structural properties of the active iodine(III) catalyst states.T he status quo of enantioselective iodine(I/III) oxidation catalysis with respect to intramolecular and intermolecular reaction control is reviewed, and specific aspects of the individual catalytic cycles are discussed.
1I ntroduction 2C hiral Aryliodine Catalysts 3E nantioselective Catalysis 3.1 Catalytic DearomatizationReactions 3.2 Formal C(sp 3 )Functionalization 3.3 Difunctionalization of Alkenes 4C onclusionScheme 14. Aryliodine-catalyzede nantioselective intermolecular para-dearomatization of phenols and aniline.Scheme15. Aryliodine-catalyzed enantioselective intermolecular para-dearomatization by Maruoka.Scheme30. Catalytic enantioselective version of the aminofluorination reaction.Scheme 28. Enantioselectiveo xidative cyclization of w-alkenylcarboxylic acids.Scheme29. Catalytic intramolecular diaminationo fa lkenes.
Ligand-free manganese-catalyzed homocoupling of arenes or aryl halides can be carried out under aerobic conditions via the in situ formation of the corresponding aryllithiums. A wide range of biaryls and derivatives has been obtained and a mechanism involving monomeric manganese-oxo complexes has been proposed on the basis of DFT calculations.
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