Enantioselective Diamination with Novel Chiral Hypervalent Iodine Catalysts

Enantioselective Prévost and Woodward reactions using chiral hypervalent iodine(III): switchover of stereochemical course of an optically active 1,3-dioxolan-2-yl cation.

Optically active 1,3-dioxolan-2-yl cation intermediates were generated during enantioselective dioxyacetylation of alkene with chiral hypervalent iodine(III). Regioselective attack of a nucleophile toward the intermediate resulted in reversal of enantioselectivity of the dioxyacetylation.

Diastereoselective aminooxygenation and diamination of alkenes with amidines by hypervalent iodine(III) reagents.

Diastereoselective anti-aminooxygenation and anti-diamination of alkenes with amidines were enabled by hypervalent iodine(III) reagents such as PhI(OCOR)2 and PhI(NMs2)2, respectively. The present transformation offers diastereochemically pure dihydroimidazoles divergently from E- and Z-alkenes.

Enantioselective Oxidative Rearrangements with Chiral Hypervalent Iodine Reagents

A stereoselective hypervalent iodine-promoted oxidative rearrangement of 1,1-disubstituted alkenes has been developed. This practically simple protocol provides access to enantioenriched α-arylated ketones without the use of transition metals from readily accessible alkenes.

Enantioselective dioxytosylation of styrenes using lactate-based chiral hypervalent iodine(III)

A series of optically active hypervalent iodine(III) reagents prepared from the corresponding (R)-2-(2-iodophenoxy)propanoate derivative was employed for the asymmetric dioxytosylation of styrene and its derivatives. The electrophilic addition of the hypervalent iodine(III) compound toward styrene proceeded with high enantioface selectivity to give 1-aryl-1,2-di(tosyloxy)ethane with an enantiom...

A chiral hypervalent iodine(III) reagent for enantioselective dearomatization of phenols.