Innenrücktitelbild: Metall- und reagensfreie dehydrierende formale Benzyl-Aryl-Kreuzkupplung durch anodische Aktivierung in 1,1,1,3,3,3-Hexafluorpropan-2-ol (Angew. Chem. 37/2018)

Dehydrierende anodische C‐C‐Kupplung von Phenolen mit elektronenziehenden Substituenten

Metal- and Reagent-Free Dehydrogenative Formal Benzyl-Aryl Cross-Coupling by Anodic Activation in 1,1,1,3,3,3-Hexafluoropropan-2-ol

A selective dehydrogenative electrochemical functionalization of benzylic positions that employs 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) has been developed. The electrogenerated products are versatile intermediates for subsequent functionalizations as they act as masked benzylic cations that can be easily activated. Herein, we report a sustainable, scalable, and reagent- and metal-free dehydrogenative formal benzyl-aryl cross-coupling. Liberation of the benzylic cation was accomplished through the use of acid. Valuable diarylmethanes are accessible in the presence of aromatic nucleophiles. The direct application of electricity enables a safe and environmentally benign chemical transformati…

A Decade of Electrochemical Dehydrogenative C,C-Coupling of Aryls.

The importance of sustainable and green synthetic protocols for the synthesis of fine chemicals has rapidly increased during the last decades in an effort to reduce the use of fossil fuels and other finite resources. The replacement of common reagents by electricity provides a cost- and atom-efficient, environmentally friendly, and inherently safe access to novel synthetic routes. The selective formation of carbon-carbon bonds between two distinct substrates is a crucial tool in organic chemistry. This fundamental transformation enables access to a broad variety of complex molecular architectures. In particular, the aryl-aryl bond formation has high significance for the preparation of organ…

Metall- und reagensfreie dehydrierende formale Benzyl-Aryl-Kreuzkupplung durch anodische Aktivierung in 1,1,1,3,3,3-Hexafluorpropan-2-ol

Electrochemical C−H Functionalization of (Hetero)Arenes—Optimized by DoE

Abstract A novel approach towards the activation of different arenes and purines including caffeine and theophylline is presented. The simple, safe and scalable electrochemical synthesis of 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) aryl ethers was conducted using an easy electrolysis setup with boron‐doped diamond (BDD) electrodes. Good yields up to 59 % were achieved. Triethylamine was used as a base as it forms a highly conductive media with HFIP, making additional supporting electrolytes superfluous. The synthesis was optimized using Design of Experiment (DoE) techniques giving a detailed insight to the significance of the reaction parameters. The mechanism was investigated by cyclic volt…

Inside Back Cover: Metal- and Reagent-Free Dehydrogenative Formal Benzyl-Aryl Cross-Coupling by Anodic Activation in 1,1,1,3,3,3-Hexafluoropropan-2-ol (Angew. Chem. Int. Ed. 37/2018)

Electrochemical Synthesis of Fluorinated Orthoesters from 1,3‐Benzodioxoles

Abstract Invited for this month's cover picture is the group of Professor Siegfried Waldvogel. The cover picture displays the robustness achieved by the installation of fluorinated alcohols on 1,3‐benzodioxoles, protecting the obtained orthoesters against acids and bases, like the shield of a knight. The simple protocol allows access to interesting compounds, whose lipophilicity is tremendously increased by the incorporation of fluorinated groups. This makes it possible to adjust the physicochemical properties of the biologically active 1,3‐benzodioxole motif. The surprisingly high stability against acids and bases gives rise to subsequent functionalizations or direct application in medicin…

Dehydrogenative Anodic Cyanation Reaction of Phenols in Benzylic Positions

Front Cover: Electrochemical Synthesis of Fluorinated Orthoesters from 1,3‐Benzodioxoles (ChemistryOpen 9/2019)

The Front Cover shows the robustness achieved by the installation of fluorinated alcohols on 1,3‐benzodioxoles, which appears like the shield of a knight protecting the obtained orthoesters against acids and bases. The simple protocol allows access to interesting compounds, whose lipophilicity is tremendously increased by the incorporation of fluorinated groups. This makes it possible to adjust the physicochemical properties of the biologically active 1,3‐benzodioxole motif. The surprisingly high stability against acids and bases gives rise to subsequent functionalizations or direct application in medicinal or agrochemistry. More information can be found in the Communication by J. L. Röckl …

Dehydrogenative Anodic C−C Coupling of Phenols Bearing Electron‐Withdrawing Groups

Abstract We herein present a metal‐free, electrosynthetic method that enables the direct dehydrogenative coupling reactions of phenols carrying electron‐withdrawing groups for the first time. The reactions are easy to conduct and scalable, as they are carried out in undivided cells and obviate the necessity for additional supporting electrolyte. As such, this conversion is efficient, practical, and thereby environmentally friendly, as production of waste is minimized. The method features a broad substrate scope, and a variety of functional groups are tolerated, providing easy access to precursors for novel polydentate ligands and even heterocycles such as dibenzofurans.

Electrosynthesis 2.0 in 1,1,1,3,3,3-hexafluoroisopropanol/amine mixtures

CCDC 1840041: Experimental Crystal Structure Determination

Related Article: Yasushi Imada, Johannes L. Röckl, Anton Wiebe, Tile Gieshoff, Dieter Schollmeyer, Kazuhiro Chiba, Robert Franke, Siegfried R. Waldvogel|2018|Angew.Chem.,Int.Ed.|57|12136|doi:10.1002/anie.201804997

CCDC 1920411: Experimental Crystal Structure Determination

Related Article: Johannes L. Röckl, Dieter Schollmeyer, Robert Franke, Siegfried R. Waldvogel|2020|Angew.Chem.,Int.Ed.|59|315|doi:10.1002/anie.201910077

CCDC 1903303: Experimental Crystal Structure Determination

Related Article: Johannes L. Röckl, Adrian V. Hauck, Dieter Schollmeyer, Siegfried R. Waldvogel|2019|ChemistryOpen|8|1167|doi:10.1002/open.201900127

CCDC 1920412: Experimental Crystal Structure Determination

Related Article: Johannes L. Röckl, Dieter Schollmeyer, Robert Franke, Siegfried R. Waldvogel|2020|Angew.Chem.,Int.Ed.|59|315|doi:10.1002/anie.201910077

CCDC 1988067: Experimental Crystal Structure Determination

Related Article: Maurice Dörr, Johannes L. Röckl, Jonas Rein, Dieter Schollmeyer, Siegfried R. Waldvogel|2020|Chem.-Eur.J.|26|10195|doi:10.1002/chem.202001171

CCDC 1920410: Experimental Crystal Structure Determination

Related Article: Johannes L. Röckl, Dieter Schollmeyer, Robert Franke, Siegfried R. Waldvogel|2020|Angew.Chem.,Int.Ed.|59|315|doi:10.1002/anie.201910077

CCDC 1840040: Experimental Crystal Structure Determination

Related Article: Yasushi Imada, Johannes L. Röckl, Anton Wiebe, Tile Gieshoff, Dieter Schollmeyer, Kazuhiro Chiba, Robert Franke, Siegfried R. Waldvogel|2018|Angew.Chem.,Int.Ed.|57|12136|doi:10.1002/anie.201804997