Electrochemical cascade migratory versus ortho-cyclization of 2-alkynylbenzenesulfonamides

Efficient control over several possible reaction pathways of free radicals is the chemical basis of their highly selective transformations. Among various competing reaction pathways, sulfonimidyl radicals generated from the electrolysis of 2-alkynylbenzenesulfonamides undergo cascade migratory or ortho-cyclization cyclization selectively.

Screening seven-electron boron-centered radicals for dinitrogen activation

The activation of dinitrogen is significant as nitrogen-containing compounds play an important role in industries. However, the inert NN triple bond caused by its large HOMO-LUMO gap (10.8 eV) and high bond dissociation energy (945 kJ mol−1) renders its activation under mild conditions particularly challenging. Recent progress shows that a few main group species can mimic transition metal complexes to activate dinitrogen. Here, we demonstrate that a series of seven-electron (7e) boron-centered radical can be used to activate N2 via density functional theory calculations.

Could π-aromaticity cross an unsaturated system to a fully saturated one?

The classification of π-/σ-aromaticity depends on the electrons with the dominating contributions. Traditionally, π- and σ-aromaticity are used to describe the unsaturated and saturated systems, respectively. Thus, it is rarely reported that π-aromaticity is dominated in a saturated system. Here we demonstrate that π-aromaticity could be dominating in several fully saturated four-membered rings (4MRs), supported by various aromaticity indices including ΔBL, NICS, EDDB, MCI, and AdNDP.