Installation of Amine Moieties into a Polycyclic Anodic Product Derived from 2,4‐Dimethylphenol

Barjau, Joaquin; Fleischhauer, J.; Schnakenburg, Gregor; Waldvogel, Siegfried R.

doi:10.1002/chem.201102722

Cited by 18 publications

(12 citation statements)

References 54 publications

(38 reference statements)

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“…The reaction conditions were chosen on the basis of previous publications . Boron-doped diamond (BDD) as the anode material has proven its outstanding performance in anodic C–C coupling in many cases. ,− Additionally, the use of HFIP as the solvent is mandatory in electro-organic coupling reactions, as it is considered essential for obtaining the desired reaction selectivity. ,− By hydrogen bonding, the oxygen functionality is blocked, avoiding the typical C–O bond formation and/or the generation of polycyclic molecular architectures. ,− …”

Section: Resultsmentioning

confidence: 99%

Supporting-Electrolyte-Free and Scalable Flow Process for the Electrochemical Synthesis of 3,3′,5,5′-Tetramethyl-2,2′-biphenol

Selt

Franke

Waldvogel

2020

Org. Process Res. Dev.

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The most efficient electrochemical synthesis of 3,3′,5,5′-tetramethyl-2,2′-biphenol by dehydrogenative coupling is reported. The electrolysis is performed supporting-electrolyte-free in 1,1,1,3,3,3-hexafluoroisopropanol and at carbon electrodes, whereby glassy carbon electrodes turned out to be superior. To provide sufficient conductivity, pyridine is added, and it can easily be recovered by evaporation and reused. This facilitates the downstream process tremendously, making it simple, economical, and technically viable. The scalability was proven by establishing a flow electrolysis in differently sized narrow-gap flow electrolyzers. Carrying out a multistep cascade electrolysis enabled the challenging hydrogen evolution to be successfully addressed. The scaled-up electrolysis provided an isolated yield of 59% biphenol.

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Section: Resultsmentioning

confidence: 99%

Supporting-Electrolyte-Free and Scalable Flow Process for the Electrochemical Synthesis of 3,3′,5,5′-Tetramethyl-2,2′-biphenol

Selt

Franke

Waldvogel

2020

Org. Process Res. Dev.

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“…Treatment with NH 4 F or amines in the presence of a CsF promotor yielded amino-functionalized Pummerer ketones (e.g., 183.5 and 183.6 ). 511 Treatment with anisole in the presence of BF 3 ·OEt 2 gave Friedel–Crafts product 183.7 , a scaffold which is remarkably similar to naturally occurring rocaglamide—an antileukemic flavagline. 512 Finally, treatment with ketones or isocyanates in the presence of BF 3 ·OEt 2 led to [3+2] cycloaddition products (e.g., 183.8 ).…”

Section: O -Centered Radical Generation From O–h Bonds Through Photochemical and Electrochemical Pcet Processesmentioning

confidence: 97%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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We present here a review of the photochemical and electrochemical applications of multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms in which both an electron and a proton are exchanged together, often in a concerted elementary step. As such, MS-PCET can function as a non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from a wide variety of common organic functional groups. We present an introduction to MS-PCET and a practitioner’s guide to reaction design, with an emphasis on the unique energetic and selectivity features that are characteristic of this reaction class. We then present chapters on oxidative N–H, O–H, S–H, and C–H bond homolysis methods, for the generation of the corresponding neutral radical species. Then, chapters for reductive PCET activations involving carbonyl, imine, other X=Y π-systems, and heteroarenes, where neutral ketyl, α-amino, and heteroarene-derived radicals can be generated. Finally, we present chapters on the applications of MS-PCET in asymmetric catalysis and in materials and device applications. Within each chapter, we subdivide by the functional group undergoing homolysis, and thereafter by the type of transformation being promoted. Methods published prior to the end of December 2020 are presented.

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“…The electron‐rich properties associated with phenolic compounds make them particularly amenable to oxidation, a feature that makes them especially attractive in natural product synthesis . Early studies by the Waldvogel laboratory have demonstrated that phenols can be electro‐oxidatively coupled to produce biphenols as well as polycyclic scaffolds . A related strategy was recently employed by the Opatz and Waldvogel groups in the syntheses of (−)‐thebaine and (−)‐oxycodone .…”

Section: Anodic Oxidationmentioning

confidence: 99%

Organic Electrosynthesis: Applications in Complex Molecule Synthesis

2019

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Organic electrosynthesis is an enabling and sustainable technology, which constitutes a rapidly expanding field of research. Electrochemical approaches serve as convenient and green alternatives to stoichiometric and toxic chemical redox agents. Electrosynthesis constitutes a promising platform for harnessing the unique reactivity profiles of radical intermediates, expediting the development of new reaction manifolds. This Review highlights both anodic and cathodic methods for the construction of various kinds of complex molecules.

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Installation of Amine Moieties into a Polycyclic Anodic Product Derived from 2,4‐Dimethylphenol

Cited by 18 publications

References 54 publications

Supporting-Electrolyte-Free and Scalable Flow Process for the Electrochemical Synthesis of 3,3′,5,5′-Tetramethyl-2,2′-biphenol

Supporting-Electrolyte-Free and Scalable Flow Process for the Electrochemical Synthesis of 3,3′,5,5′-Tetramethyl-2,2′-biphenol

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Organic Electrosynthesis: Applications in Complex Molecule Synthesis

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