A5039373286- Sulfur-Based Synthesis Techniques
- Catalytic C–H Functionalization Methods
- Radical Photochemical Reactions
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Oxidative Organic Chemistry Reactions
- Silicone and Siloxane Chemistry
- Molecular spectroscopy and chirality
- Cyclopropane Reaction Mechanisms
- Crystallography and molecular interactions
- Chemical Reaction Mechanisms
- Analytical Chemistry and Chromatography
- Catalytic Alkyne Reactions
- Catalytic Cross-Coupling Reactions
- Vanadium and Halogenation Chemistry
- Organoboron and organosilicon chemistry
- Synthesis and Catalytic Reactions
- Asymmetric Hydrogenation and Catalysis
- Synthesis and characterization of novel inorganic/organometallic compounds
- Polyoxometalates: Synthesis and Applications
- Chemical Synthesis and Analysis
- Coordination Chemistry and Organometallics
- Synthetic Organic Chemistry Methods
- Chemical Reactions and Isotopes
- Organic Chemistry Cycloaddition Reactions
University of Wisconsin–Madison
2021-2024
Zero to Three
2024
Robert Bosch (Germany)
2024
University of California, Davis
2019-2021
Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C–H amination strategies remain limited with respect the viable N-substituents. Herein, we disclose a new electrochemical process prepare aliphatic by coupling two abundant starting materials: secondary and unactivated alkenes. This oxidative transformation proceeds via generation of an electrophilic adduct between thianthrene alkene substrates. Treatment these adducts...
We describe a photocatalytic system that reveals latent photooxidant behavior from one of the most reducing conventional photoredox catalysts, N-phenylphenothiazine (PTH). This aerobic photochemical reaction engages difficult to oxidize feedstocks, such as benzene, in C(sp2)–N coupling reactions through direct oxidation. Mechanistic studies are consistent with activation PTH via photooxidation and Lewis acid cocatalysts scavenging inhibitors inextricably formed this process.
Abstract Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes a limited array of substituents, difficult scale, or both. Herein, we disclose new cyclopropane synthesis through the formal coupling abundant carbon pronucleophiles unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis thianthrene presence substrates. We find that these...
A detailed mechanistic study of the Z-selective allylic functionalization via thianthrenium salts is presented. Kinetic analyses, deuterium labeling experiments, and computational methods are used to rationalize observed reactivity selectivity. We find that reaction proceeds a rate-determining stereodetermining deprotonation an alkenylthianthrenium species. The Z-configuration resultant ylide translated into Z-allylic amine product through sequence subsequent fast irreversible steps:...
The hydrogen-bond-accepting abilities for more than 100 organic molecules are quantified using 19F and 31P NMR spectroscopy with pentafluorobenzoic acid (PFBA) phenylphosphinic (PPA) as commercially available, inexpensive probes. Analysis of pyridines anilines a variety electronic modifications demonstrates that changes in shifts can predict the secondary effects contribute to H-bond-accepting ability, establishing ability PFBA PPA binding trends. various metal-chelating ligands...
Abstract The catalytic activity, kinetics, and quantification of H‐bonding ability incompletely condensed polyhedral oligomeric silsesquioxane (POSS) silanols are reported. POSS‐triols, a homogeneous model for vicinal silica surface sites, exhibit enhanced compared with other alcohols as quantified using 31 P NMR probe. Evaluation Friedel–Crafts addition reaction shows that phenyl‐POSS‐triol is active an H‐bond donor catalyst whereas POSS studied not. An in‐depth kinetic study (using RPKA...
A detailed mechanistic study of the Z-selective allylic functionalization via thianthrenium salts is presented. We have leveraged kinetic analysis and deuterium labeling to concretely determine each elementary steps involved used computational methods establish a high-resolution model rationalize observed reactivity selectivity. find that reaction proceeds rate- stereodetermining deprotonation an alkenylthianthrenium species. The Z-configuration resultant ylide translated into final...
We describe a photocatalytic system that reveals latent photooxidant behavior from one of the most reducing conventional photoredox catalysts, <i>N</i>-phenylphenothiazine<i> </i>(<b>PTH</b>). This aerobic photochemical reaction engages difficult to oxidize feedstocks, such as benzene, in C(sp<sup>2</sup>)–N coupling reactions through direct oxidation. Mechanistic studies are consistent with activation <b>PTH</b> via photooxidation...
We report carbene insertion into Si-H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze aryl-diazoacetates as precursors to afford POSS structures containing both ester and aryl groups orthogonal functional handles further derivatization materials. Four diverse structurally varied silsesquioxane core scaffolds with one, three, or eight were evaluated diazo reactants produce a total 20 new...
Abstract Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes a limited array of substituents, difficult scale, or both. Herein, we disclose new cyclopropane synthesis through the formal coupling abundant carbon pronucleophiles unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis thianthrene presence substrates. We find that these...
Abstract Oxidative alkene functionalization reactions are a fundamental class of complexity‐building organic transformations. However, the majority established approaches rely on electrophilic reagents that limit diversity groups can be installed. Recent advances have new approach instead relies transformation alkenes into thianthrene‐derived cationic electrophiles. These linchpin intermediates generated selectively and undergo diverse array mechanistically distinct with abundant...
family of visible light organic photoswitches, i.
… for biomedical applications is featured on the cover and discussed in Review by Younan Xia et al. (e202319567).Central to image are infographic illustrations of an atom, a heart, DNA helix, blood vessel top microscope, indicating focus research applications.These surrounded four circular vignettes, each containing schematics representing form hybrid nanomaterials, including nanostructures, nanocomposites, metalorganic frameworks, biohybrids. Organic MaterialsAn octupolar design paradigm...
Abstract We report carbene insertion into Si−H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze aryl‐diazoacetates as precursors to afford POSS structures containing both ester and aryl groups orthogonal functional handles further derivatization materials. Four diverse structurally varied silsesquioxane core scaffolds with one, three, or eight were evaluated diazo reactants produce a...
We describe a photocatalytic system that reveals latent photooxidant behavior from one of the most reducing conventional photoredox catalysts, N -phenylphenothiazine ( PTH ). This aerobic photochemical reaction engages difficult to oxidize feedstocks, such as benzene, in C(sp 2 )–N coupling reactions through direct oxidation. Mechanistic studies are consistent with activation via photooxidation and Lewis acid co-catalysts scavenge inhibitors formed upon catalyst activation.
Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C–H amination strate-gies remain limited with respect the viable N-substituents. Herein we disclose a new electrochemical process prepare aliphatic by coupling two abundant starting materials: secondary and unactivated alkenes. This oxidative transformation proceeds via generation of an electrophilic adduct between thianthrene alkene substrates. Treatment these adducts...