Efficient and Sustainable Electrosynthesis of N-Sulfonyl Iminophosphoranes by the Dehydrogenative P-N Coupling Reaction.

Iminophosphoranes are commonly used reagents in organic synthesis and are, therefore, of great interest. An efficient and sustainable iodide-mediated electrochemical synthesis of N-sulfonyl iminophosphoranes from readily available phosphines and sulfonamides is reported. This method features low amounts of supporting electrolytes, inexpensive electrode materials, a simple galvanostatic setup, and high conversion rates. The broad applicability could be demonstrated by synthesizing 20 examples in yields up to 90%, having diverse functional groups including chiral moieties and biologically relevant species. Furthermore, electrolysis was performed on a 20 g scale and could be run in repetitive mode by recycling the electrolyte, which illustrates the suitability for large-scale production. A reaction mechanism involving electrochemical mediation by the iodide-based supporting electrolyte is proposed, completely agreeing with all of the results.

Dehydrogenative Electrochemical Synthesis of N-Aryl-3,4-Dihydroquinolin-2-ones by Iodine(III)-Mediated Coupling Reaction.

Electrochemically generated hypervalent iodine(III) species are powerful reagents for oxidative C-N coupling reactions, providing access to valuable N-heterocycles. A new electrocatalytic hypervalent iodine(III)-mediated in-cell synthesis of 1H-N-aryl-3,4-dihydroquinolin-2-ones by dehydrogenative C-N bond formation is presented. Catalytic amounts of the redox mediator, a low supporting electrolyte concentration and recycling of the solvent used make this method a sustainable alternative to electrochemical ex-cell or conventional approaches. Furthermore, inexpensive, readily available electrode materials and a simple galvanostatic set-up are applied. The broad functional group tolerance could be demonstrated by synthesizing 23 examples in yields up to 96 %, with one reaction being performed on a 10-fold higher scale. Based on the obtained results a sound reaction mechanism could be proposed.

Electrochemical synthesis of N,N'-disubstituted indazolin-3-ones via an intramolecular anodic dehydrogenative N-N coupling reaction.

The use of electricity as a traceless oxidant enables a sustainable and novel approach to N,N'-disubstituted indazolin-3-ones by an intramolecular anodic dehydrogenative N-N coupling reaction. This method is characterized by mild reaction conditions, an easy experimental setup, excellent scalability, and a high atom economy. It was used to synthesize various indazolin-3-one derivatives in yields up to 78%, applying inexpensive and sustainable electrode materials and a low supporting electrolyte concentration. Mechanistic studies, based on cyclic voltammetry experiments, revealed a biradical pathway. Furthermore, the access to single 2-aryl substituted indazolin-3-ones by cleavage of the protecting group could be demonstrated.