Aminoalcohols are vital motifs in chemical synthesis; however, traditional synthetic technologies relying on polar disconnections have various limitations. Now, such motifs can be expediently accessed by leveraging a radical-based approach, enabling the stereoselective preparation of an array of valuable building blocks.

Herein, we present a prominent metal-free C–N cross-coupling platform that enables access to carbamoyl- and ketoazides from isocyanides or silyl enol ethers and trimethylsilyl azide (TMSN3) with an aid of iodine(III) promoter. This offers a rapid route to a diverse set of synthetically valuable azide decorated fragments with excellent substrate scope and good to excellent yields. The disclosed platform exemplifies the use of TMSN3 for incorporation of the azide fragment without the loss of N2.

Herein, a straightforward synthetic approach for the construction of phenanthridin-6(5H)-one skeletons is disclosed. The developed protocol relies on palladium catalysis, providing controlled access to a range of functionalized phenanthridin-6(5H)-ones in 59-88% yields. Furthermore, plausible reaction pathways are proposed based on mechanistic experiments.

Establishing chemodivergent synthetic strategies remains a daunting task in the realm of free-radical reaction manifolds. In the December issue of Chem, Glorius and co-workers resolve this challenge for selective difunctionalization of aliphatic alkenes. In the disclosed light-promoted radical relay process, switchable trifluoromethylation/alkylation or trifluoromethylation/sulfonylation of alkenes is achieved.

The Wittig reaction is a valuable and powerful tool in organic synthesis, providing a convenient route from aldehydes and ketones to alkenes. Herein, a novel copper-assisted Wittig-type olefination of aldehydes with p-toluenesulfonylmethyl isocyanide (TosMIC) is disclosed, providing a direct and operationally simple approach to (E)-vinyl sulfones under mild conditions, compatible with a multitude of common functional groups. Experimental and computational investigations imply that the reaction proceeds through an intriguing electronically-controlled (3 + 2)/retro-(3 + 2) cycloaddition pathway.

A protocol for silver-catalyzed controlled intermolecular cross-coupling of silyl enolates is disclosed. The protocol displays good functional group tolerance and allows efficient preparation of a series of synthetically useful 1,4-diketones. Preliminary mechanistic investigations suggest that the reaction proceeds through a one-electron process involving free radical species in which PhBr acts as the oxidant. 

A protocol for a tandem Pd/Cu-catalyzed intermolecular cross-coupling cascade between o-bromobenzoic acids and 2-(2-bromoaryl)-1H-benzo[d]imidazoles or the corresponding imidazoles is presented. The protocol provides conceptually novel and controlled access to synthetically useful N-fused (benzo)imidazophenanthridine scaffolds with high efficiency, a broad substrate scope, and excellent functional group compatibility.