Recent developments in experimental and computational chemistry have identified a rapidly growing class of nucleophilic aromatic substitutions that proceed by concerted (cSNAr) rather than classical, two‐step, SNAr mechanisms. Whereas traditional SNAr reactions require substantial activation of the aromatic ring by electron‐withdrawing substituents, such activating groups are not mandatory in the concerted pathways.

A synthetic method of isoquinolines from aryl ketone O-acyloxime derivatives and internal alkynes has been developed using [Cp*RhCl(2)](2)-NaOAc as the potential catalyst system. The present transformation is carried out by a redox-neutral sequence of C-H vinylation via ortho-rhodation and C-N bond formation of the putative vinyl rhodium intermediate on the oxime nitrogen, where the N-O bond of oxime derivatives could work as an internal oxidant to maintain the catalytic cycle.

A method for aliphatic C-H bond oxidation of oximes and hydrazones mediated by 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) has been developed, which enables the concise assembly of substituted isoxazole and pyrazole skeletons.

This review updates on recent advances in aliphatic sp(3) C-H bond oxidation by remote H-radical abstraction with oxygen- and nitrogen-radicals classifying by the type of the radical precursors.

Transition-metal catalyzed cross-coupling reactions have created an epoch in modern synthetic organic chemistry, offering a variety of insights in retrosynthetic tactics to synthesize targeted complex molecules in medicine and materials-based applications. Despite numerous types of combinations between nucleophiles, electrophiles, and transition-metal catalysts available for the cross-coupling reactions, construction of covalent bonds including sp 3 -hybridized carbon(s) still remains a challenge due to the inherent diverse reactivity of the alkyl species (i.e. alkyl halides, alkyl metals) involved in the catalytic cycle. To realize this goal, the methods to leverage alkyl radicals have recently emerged. This perspective highlights and discusses recent advances on transition-metal catalyzed cross coupling reactions that engage alkyl radicals for C(sp 3 )-N and C(sp 3 )-Si bond formation with alkyl halides as well as use of carboxylic acid derivatives as surrogates of alkyl halides in decarboxylative C(sp 3 )-C(sp 2 )/C(sp 3 )/B couplings.