A5084236752- Chemical Reactions and Mechanisms
- Advanced Chemical Physics Studies
- Sulfur-Based Synthesis Techniques
- Catalytic Cross-Coupling Reactions
- Radical Photochemical Reactions
- Molecular Spectroscopy and Structure
- Molecular Junctions and Nanostructures
- Lanthanide and Transition Metal Complexes
- Chemical Reaction Mechanisms
- Cyclopropane Reaction Mechanisms
- Chemical Reactions and Isotopes
- CO2 Reduction Techniques and Catalysts
- Organometallic Complex Synthesis and Catalysis
- Photochemistry and Electron Transfer Studies
Ruhr University Bochum
2020-2023
Scripps (United States)
2023
Scripps Institution of Oceanography
2023
Scripps Research Institute
2022
The Kolbe reaction forms carbon-carbon bonds through electrochemical decarboxylative coupling. Despite more than a century of study, the has seen limited applications owing to extremely poor chemoselectivity and reliance on precious metal electrodes. In this work, we present simple solution long-standing challenge: Switching potential waveform from classical direct current rapid alternating polarity renders various functional groups compatible enables sustainable carbon-based electrodes...
ConspectusA decisive factor for obtaining high yields and selectivities in organic synthesis is the choice of proper solvent. Solvent selection often guided by intuitive understanding transition state–solvent interactions. However, quantum-mechanical tunneling can significantly contribute to chemical reactions, circumventing state thus depriving chemists their handle on reaction kinetics. In this Account, we aim provide rationales effects solvation reactions derived from experiments...
Abstract The equilibrium between benzene oxide ( 1 ) and oxepin 2 is of large importance for understanding the degradation in biological systems troposphere. Our studies reveal that at cryogenic temperatures, this equilibration governed by rare heavy‐atom tunneling. In solid argon 3 K, rearranges to via tunneling with a rate constant approximately 5.3×10 −5 s −1 . Thus, nonpolar environment, slightly more stable than , agreement calculations CCSD(T) level theory. However, if doped % H O or...
The ring-opening of a highly strained cyclopropene to carbene proceeds via heavy-atom tunneling. This rearrangement is accelerated in the presence H 2 O, ICF 3 or BF , resulting novel Lewis-acid catalyzed tunneling reaction.
Heavy-atom tunneling limits the lifetime and observability of bicyclo[4.1.0]hepta-2,4,6-triene, a key intermediate in rearrangement phenylcarbene. Bicyclo[4.1.0]hepta-2,4,6-triene had been proposed as primary phenylcarbene, but despite many efforts evaded its characterization even cryogenic matrices. By introducing fluorine substituents into ortho-positions phenyl ring highly strained cyclopropene 1,5-difluorobicyclo[4.1.0]hepta-2,4,6-triene becomes stable enough to be characterized argon...
Abstract The equilibrium between benzene oxide ( 1 ) and oxepin 2 is of large importance for understanding the degradation in biological systems troposphere. Our studies reveal that at cryogenic temperatures, this equilibration governed by rare heavy‐atom tunneling. In solid argon 3 K, rearranges to via tunneling with a rate constant approximately 5.3×10 −5 s −1 . Thus, nonpolar environment, slightly more stable than , agreement calculations CCSD(T) level theory. However, if doped % H O or...
Abstract Heavy‐atom tunneling limits the lifetime and observability of bicyclo[4.1.0]hepta‐2,4,6‐triene, a key intermediate in rearrangement phenylcarbene. Bicyclo[4.1.0]hepta‐2,4,6‐triene had been proposed as primary phenylcarbene, but despite many efforts evaded its characterization even cryogenic matrices. By introducing fluorine substituents into ortho ‐positions phenyl ring highly strained cyclopropene 1,5‐difluorobicyclo[4.1.0]hepta‐2,4,6‐triene becomes stable enough to be...
The Kolbe reaction has seen limited applications owing to its extremely poor chemoselectivity and reliance on precious metal-based electrodes, despite potential be one of the workhorse reactions organic synthesis for C–C bond formation in both discovery process settings. Although hundreds studies over a century aimed improve efficiency selectivity, general solutions have yet found. Herein, an exceedingly simple solution this long-standing challenge is presented by merely tuning waveform...
Nichtkovalente Wechselwirkungen Basierend auf Matrixisolationsstudien entlarven W. Sander et al. in ihrer Zuschrift S. 20498 ein seit langem bestehendes Missverständnis bezüglich des Benzoloxid-Oxepin-Gleichgewichts, indem sie die intrinsisch größere Stabilität Oxepins beweisen.
The Kolbe reaction has seen limited applications owing to its extremely poor chemoselectivity and reliance on precious metal-based electrodes, despite potential be one of the workhorse reactions organic synthesis for C–C bond formation in both discovery process settings. Although hundreds studies over a century aimed improve efficiency selectivity, general solutions have yet found. Herein, an exceedingly simple solution this long-standing challenge is presented by merely tuning waveform...