Metal-free, catalytic enantioselective intermolecular oxyamination of alkenes is realized by use of organoiodine(I/III) chemistry. The protocol is applicable toward aryl-and alkyl-substituted alkenes with high enantioselectivity and electronically controlled regioselectivity. The oxyaminated products can be easily deprotected in one step to reveal free amino alcohols in high yields without loss of enantioselectivity. A key to our success is the discovery of a virtually unexplored chemical entity, N-(fluorosulfonyl)carbamate, as a bifunctional N,O-nucleophile.

We report herein the development of an enantioselective oxidative para-dearomatization of sulfonanilides with water by use of an indanol-based chiral organoiodine catalyst, originally developed in our group. This reaction proceeds efficiently by the use of N-mesylprotected anilines as substrates, giving functionalized pquinol imines in good yields and moderate to high enantioselectivities.

Organoiodine-catalyzed enantioselective intramolecular oxyaminations were realized by the use of benzyl N-(fluorosulfonyl)carbamate as the exogenous nitrogen source. The method allows access to enantioenriched lactones and oxazolines, starting from γ,δ- and δ,ε-unsaturated esters and N-allyl amides, respectively.