Aktive Anode auf Molybdänbasis für dehydrierende Kupplungen

About the selectivity and reactivity of active nickel electrodes in C–C coupling reactions

Active anodes which are operating in highly stable protic media such as 1,1,1,3,3,3-hexafluoroisopropanol are rare. Nickel forms, within this unique solvent, a non-sacrificial active anode at constant current conditions, which is superior to the reported powerful molybdenum system. The reactivity for dehydrogenative coupling reactions of this novel active anode increases when the electrolyte is not stirred during electrolysis. Besides the aryl-aryl coupling, a dehydrogenative arylation reaction of benzylic nitriles was found while stirring the mixture providing quick access to synthetically useful building blocks.

Investigations on isomerization and rearrangement of polycyclic arenes under oxidative conditions – Anodic versus reagent-mediated reactions

Abstract Electro-organic conversions at an active molybdenum anode enable the formation of fused arenes. High chemoselectivity was achieved under anodic conditions, and a reagent-induced selectivity was observed by comparison with results of MoCl5-mediated reactions. Polycyclic arenes like phenanthrenes, triphenylenes, chrysenes, or helicenes were selectively obtained in yields up to 87% and in some cases unusual rearrangements were crucial for the product formation.

Mild, Fast, and Easy To Conduct MoCl5-Mediated Dehydrogenative Coupling Reactions in Flow

A convenient and straightforward approach to performing oxidative coupling reactions in flow is presented. A collection of electron-rich benzene derivatives was subjected to this protocol, and the distinct utility of molybdenum pentachloride (MoCl5) is established. Using this unexplored protocol, biphenyls could be obtained in 21–91% isolated yield. This simple protocol opens a new chapter in reagent-mediated dehydrogenative coupling reactions, and yields are compared to classical approaches.

Active Molybdenum‐Based Anode for Dehydrogenative Coupling Reactions

A new and powerful active anode system that can be operated in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) has been discovered. In HFIP the molybdenum anode forms a compact, conductive, and electroactive layer of higher-valent molybdenum species. This system can replace powerful but stoichiometrically required MoV reagents for the dehydrogenative coupling of aryls. This electrolytic reaction is more sustainable and allows the conversion of a broad scope of activated arenes.

CCDC 1882077: Experimental Crystal Structure Determination

Related Article: Sebastian B. Beil, Peter Franzmann, Timo Müller, Maximilian M. Hielscher, Tobias Prenzel, Dennis Pollok, Nicole Beiser, Dieter Schollmeyer, Siegfried R. Waldvogel|2018|Electrochimica Acta|302|310|doi:10.1016/j.electacta.2019.02.041

CCDC 1882075: Experimental Crystal Structure Determination

Related Article: Sebastian B. Beil, Peter Franzmann, Timo Müller, Maximilian M. Hielscher, Tobias Prenzel, Dennis Pollok, Nicole Beiser, Dieter Schollmeyer, Siegfried R. Waldvogel|2018|Electrochimica Acta|302|310|doi:10.1016/j.electacta.2019.02.041

CCDC 1882076: Experimental Crystal Structure Determination

Related Article: Sebastian B. Beil, Peter Franzmann, Timo Müller, Maximilian M. Hielscher, Tobias Prenzel, Dennis Pollok, Nicole Beiser, Dieter Schollmeyer, Siegfried R. Waldvogel|2018|Electrochimica Acta|302|310|doi:10.1016/j.electacta.2019.02.041

CCDC 1882073: Experimental Crystal Structure Determination

Related Article: Sebastian B. Beil, Peter Franzmann, Timo Müller, Maximilian M. Hielscher, Tobias Prenzel, Dennis Pollok, Nicole Beiser, Dieter Schollmeyer, Siegfried R. Waldvogel|2018|Electrochimica Acta|302|310|doi:10.1016/j.electacta.2019.02.041

CCDC 1976461: Experimental Crystal Structure Determination

Related Article: Sebastian B. Beil, Manuel Breiner, Lara Schulz, Aaron Schüll, Timo Müller, Dieter Schollmeyer, Alexander Bomm, Michael Holtkamp, Uwe Karst, Wolfgang Schade, Siegfried R. Waldvogel|2020|RSC Advances|10|14249|doi:10.1039/D0RA02673E

CCDC 1882074: Experimental Crystal Structure Determination

Related Article: Sebastian B. Beil, Peter Franzmann, Timo Müller, Maximilian M. Hielscher, Tobias Prenzel, Dennis Pollok, Nicole Beiser, Dieter Schollmeyer, Siegfried R. Waldvogel|2018|Electrochimica Acta|302|310|doi:10.1016/j.electacta.2019.02.041

CCDC 1882078: Experimental Crystal Structure Determination

Related Article: Sebastian B. Beil, Peter Franzmann, Timo Müller, Maximilian M. Hielscher, Tobias Prenzel, Dennis Pollok, Nicole Beiser, Dieter Schollmeyer, Siegfried R. Waldvogel|2018|Electrochimica Acta|302|310|doi:10.1016/j.electacta.2019.02.041