The heterodifunctionalization of alkenes is an efficient method for synthesizing highly functionalized organic molecules. In this report, we describe the use of anodically coupled electrolysis for the catalytic chloroalkylation of alkenes–a reaction that constructs vicinal C–C and C–Cl bonds in a single synthetic operation–from malononitriles or cyanoacetates and NaCl. Knowledge of the persistent radical effect guided the reaction design and development. A series of controlled experiments, including divided-cell electrolysis that compartmentalized the anodic and cathodic events, allowed us to identify the key radical intermediates and the pathway to their electrocatalytic formation. Cyclic voltammetry data further support the proposed mechanism entailing the parallel, Mn-mediated generation of two radical intermediates in an anodically coupled electrolysis followed by their selective addition to the alkene.
Umpolung is a classic and central concept in synthesis that produces a reversal of the normal reactivity of the molecules under study. The most straightforward method for umpolung involves an electron transfer reaction. The present study describes bidirectional access to radical cation Diels‐Alder reactions by electrocatalysis. The radical cation either of trans‐anethole or 9‐methylanthracene could trigger the reaction, which was confirmed unambiguously through the use of silica‐gel‐supported substrates.
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