A novel light-induced C─H amination of heteroarenes can be accomplished with preformed iodine(III) reagents as the combined oxidant and nitrogen source. The reaction requires the use of a small amount of molecular iodine, which under photochemical activation generates in situ an iodine(I) reagent as the initiator of the radical amination reaction. A total of 32 examples exemplify the broad scope of the transformation.

Abstract2,6‐Disubstituted anilines are readily prepared from the direct reaction between amides and diaryliodonium salts. As demonstrated for 24 different examples, the reaction is of unusually broad scope with respect to the sterically congested arene and the nitrogen source, occurs without the requirement for any additional promoter, and proceeds through a direct reductive elimination at the iodine(III) center. The efficiency of the coupling procedure is further demonstrated within the short synthesis of a chemerin binding inhibitor.

1,2-Diiodobenzene is presented as an efficient catalyst precursor for the intermolecular amination of arenes under homogeneous conditions. N-Troc and N-phthalimido-substituted methoxyamines serve as suitable nitrogen sources providing the corresponding aniline derivatives in up to 99% yield and with up to 66:1 regioselectivity. Key for this successful C-N coupling protocol is the strained µ−oxo-bridged conformation of the bisiodine(III) catalyst, which induces unparalleled high reactivity.

The reaction of allylzinc bromides with α‐acryloylamidoalkyl sulfones represents a mild and straightforward entry to the corresponding homoallylamines. These dienyl compounds successfully proceeded in a ring‐closing metathesis reaction by treatment with Grubbs II catalyst to lead to 6‐alkyltetrahydropyridin‐2‐ones. Homoallylamino derivatives that contain a branched terminal alkene moiety preferentially proceeded in cross‐metathesis reaction to give the selective formation of N‐substituted fumaramides.

To sustain innovation in glycobiology, effective routes to well-defined carbohydrate probes must be developed. For over a century, glycosylation has been dominated by the formation of the anomeric Csp -O acetal junction in glycostructures. A dissociative mechanistic spectrum spanning S 1 and S 2 is frequently operational thereby reducing the efficiency. By reengineering this fundamental process, an orthogonal disconnection allows the acetal to be formed directly from the reducing sugar without the need for substrate pre-functionalisation. The use of stable aryliodonium salts facilitates a formal O-H functionalisation reaction. This allows lactols to undergo mild, metal-free O-arylation at ambient temperature. The efficiency of the transformation has been validated using a variety of pyranoside and furanoside monosaccharides in addition to biologically relevant di- and trisaccharides (up to 85 %). Fluorinated mechanistic probes that augment the anomeric effect were employed. It is envisaged that this strategy will prove expansive for the construction of complex acetals under substrate-based stereocontrol.