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.

2,6‐Disubstituted iodoarenes bearing amide‐functionalized side arms are reported as new structures in redox‐active iodine(I/III) catalysis. In combination with bis‐sulfonimides as nitrogen sources and 3‐chloroperbenzoic acid (mCPBA) as benign terminal oxidant they catalyze the vicinal diamination of styrenes. The obtained reactivity and selectivity outperform other iodoarene catalyst candidates. This protocol provides a sustainable alternative to previous related protocols for diamination that are based on stoichiometric iodine(III) reagents.

The front cover picture is provided by Kilian Muñiz and co‐workers. “How would you like to live in Looking‐Glass House, Kitty? I wonder if they′d give you milk in there? Perhaps Looking‐Glass milk isn′t good to drink?” Alice's questions from the famous book from Lewis Carroll correlate to the expanding wonderland of powerful lactate‐based iodine catalysts. Unlike Alice's concern, these chiral iodine(I/III) compounds create the desired mirror‐image of each world with predictable stereocontrol. A state‐of‐the‐art description of the wonderland of powerful enantioselective iodine(I/III) catalysts is provided by the review of Flores et al. on pages 2–25 (A. Flores, E. Cots, J. Bergès, K. Muñiz, Adv. Synth. Catal. 2019, 361, 2–25; DOI: 10.1002/adsc.201800521).

In the course of upscaling the synthesis of enantiopure aryliodine precatalysts, we detected an unreported meso form of the catalysts for the first time. A new scalable route was developed to avoid epimerization of the lactamide arms, providing syntheses of the precatalysts that are both more effective and much less time-consuming. The catalysts obtained with these synthetic procedures have been employed in some published reactions, reaching the maximum ee ever reported.

In the search for synthetic routes for the preparation of cisand transdecahydroquinolin-2-ones, a procedure for the generation of enantiopure trans-hydrochromene lactones, by treatment of (R)-phenylglycinol-derived oxazoloquinolone lactams with Na/liq. NH3 followed by acidification, has been developed.