A useful protocol for achieving decarboxylative cross-coupling
(DCC) of redox-active esters (RAE, isolated or generated in situ)
and halo(hetero)arenes is reported. This pragmatically focused study
employs a unique Ag–Ni electrocatalytic platform to overcome
numerous limitations that have plagued this strategically powerful
transformation. In its optimized form, coupling partners can be combined
in a surprisingly simple way: open to the air, using technical-grade
solvents, an inexpensive ligand and Ni source, and substoichiometric
AgNO3, proceeding at room temperature with a simple commercial
potentiostat. Most importantly, all of the results are placed into
context by benchmarking with state-of-the-art methods. Applications
are presented that simplify synthesis and rapidly enable access to
challenging chemical space. Finally, adaptation to multiple scale
regimes, ranging from parallel milligram-based synthesis to decagram
recirculating flow is presented.
Chalcogen bonding is important in numerous aspects of chemistry, both in the solid state and in solution. Surveying the literature, it becomes clear that during its rebranding from chalcogen–chalcogen interactions, some parts of the community have somewhat neglected to recall its discovery and the initial studies referring to it in its previous guise. In this Viewpoint, we trace the path of research into this phenomenon, from its discovery, through its renaming, and to some of the varied and interesting chemistry it has led to so far, ranging from crystal engineering through supramolecular assembly to modern catalysis.
We describe the first electrochemical activation of D–A cyclopropanes and D–A cyclobutanes leading after C(sp3)−C(sp3) cleavage to the formation of highly reactive radical cations. This concept is utilized to formally insert molecular oxygen after direct or DDQ‐assisted anodic oxidation of the strained carbocycles, delivering β‐ and γ‐hydroxy ketones and 1,2‐dioxanes electrocatalytically. Furthermore, insights into the mechanism of the oxidative process, obtained experimentally and by additional quantum‐chemical calculations are presented. The synthetic potential of the reaction products is demonstrated by diverse derivatizations.
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