A5068620047- Radical Photochemical Reactions
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Catalytic C–H Functionalization Methods
- Sulfur-Based Synthesis Techniques
- Crystallography and molecular interactions
- CO2 Reduction Techniques and Catalysts
- Catalytic Cross-Coupling Reactions
- Electrochemical Analysis and Applications
- Oxidative Organic Chemistry Reactions
- Electrocatalysts for Energy Conversion
- Click Chemistry and Applications
- Asymmetric Hydrogenation and Catalysis
- Molecular Junctions and Nanostructures
- Asymmetric Synthesis and Catalysis
- Synthesis and Catalytic Reactions
- Advanced biosensing and bioanalysis techniques
- Ammonia Synthesis and Nitrogen Reduction
- Chemical Synthesis and Reactions
- Protein Degradation and Inhibitors
- Semiconductor materials and devices
- Conducting polymers and applications
- Chemical Synthesis and Analysis
- Cyclopropane Reaction Mechanisms
- Vanadium and Halogenation Chemistry
Scripps Research Institute
2014-2025
Torrey Pines Institute For Molecular Studies
2019-2025
Scripps (United States)
2019-2025
Scripps Institution of Oceanography
2019-2025
Hiroshima University
2019-2023
Chungbuk National University
2019
Kyoto University
2011-2018
Chiba University
2016
A practical electrochemical oxidation of unactivated C–H bonds is presented. This reaction utilizes a simple redox mediator, quinuclidine, with inexpensive carbon and nickel electrodes to selectively functionalize "deep-seated" methylene methine moieties. The process exhibits broad scope good functional group compatibility. scalability, as illustrated by 50 g scale sclareolide, bodes well for immediate widespread adoption.
Reductive electrosynthesis has faced long-standing challenges in applications to complex organic substrates at scale. Here, we show how decades of research lithium-ion battery materials, electrolytes, and additives can serve as an inspiration for achieving practically scalable reductive electrosynthetic conditions the Birch reduction. Specifically, demonstrate that using a sacrificial anode material (magnesium or aluminum), combined with cheap, nontoxic, water-soluble proton source...
C–N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- Cu-based catalytic systems, it has proven to be a staple transformation for those both academia industry. The current study presents development mechanistic understanding an electrochemically driven, Ni-catalyzed method achieving this reaction high strategic importance. Through series electrochemical, computational, kinetic, empirical experiments, key features have...
Along with amide bond formation, Suzuki cross-coupling, and reductive amination, the Buchwald-Hartwig-Ullmann-type amination of aryl halides stands as one most employed reactions in modern medicinal chemistry. The work herein demonstrates potential utilizing electrochemistry to provide a complementary avenue access such critical bonds using an inexpensive nickel catalyst under mild reaction conditions. Of note is scalability, functional-group tolerance, rapid rate, ability employ variety...
Driven by the ever-increasing pace of drug discovery and need to push boundaries unexplored chemical space, medicinal chemists are routinely turning unusual strained bioisosteres such as bicyclo[1.1.1]pentane, azetidine, cyclobutane modify their lead compounds. Too often, however, difficulty installing these fragments surpasses challenges posed even construction parent scaffold. This full account describes development application a general strategy where spring-loaded, C–C C–N bonds react...
Unlike its other halogen atom siblings, the utility of chlorinated arenes and (hetero)arenes are twofold: they useful in tuning electronic structure as well acting points for diversification via cross-coupling. Herein we report invention a new guanidine-based chlorinating reagent, CBMG or "Palau'chlor", inspired by key chlorospirocyclization en route to pyrrole imidazole alkaloids. This direct, mild, operationally simple, safe method is compatible with range nitrogen-containing heterocycles...
Challenges in the selective manipulation of functional groups (chemoselectivity) organic synthesis have historically been overcome either by using reagents/catalysts that tunably interact with a substrate or through modification to shield undesired sites reactivity (protecting groups). Although electrochemistry offers precise redox control achieve unique chemoselectivity, this approach often becomes challenging presence multiple redox-active functionalities. Historically, electrosynthesis...
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...
Conventional chemical and even electrochemical Birch-type reductions suffer from a lack of chemoselectivity due to reliance on alkali metals or harshly reducing conditions. This study reveals that simpler avenue is available for such by simply altering the waveform current delivery, namely rapid alternating polarity (rAP). The developed method solves these issues, proceeding in protic solvent, can be easily scaled up without any metal additives stringently anhydrous
A mild, scalable (kg) metal-free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access valuable from simple acid feedstocks. This robust method relies on alternating polarity maintain the quality electrode surface local pH, providing a deeper understanding Hofer-Moest process with unprecedented chemoselectivity.
The synthesis of quaternary carbons often requires numerous steps and complex conditions or harsh reagents that act on heavily engineered substrates. This is largely a consequence conventional polar-bond retrosynthetic disconnections in turn require multiple functional group interconversions, redox manipulations, protecting chemistry. Here, we report simple catalyst reductant combination converts two types feedstock chemicals, carboxylic acids olefins, into tetrasubstituted through...
Chiral electrophilic selenium catalysts have been applied to catalytic asymmetric transformations of alkenes over the past two decades. However, highly enantioselective reactions with a broad substrate scope not yet developed. We report first successful example this reaction employing catalyst based on rigid indanol scaffold, which can be easily synthesized from commercially available indanone. The efficiently converts β,γ-unsaturated carboxylic acids into various enantioenriched...
Abstract Along with amide bond formation, Suzuki cross‐coupling, and reductive amination, the Buchwald–Hartwig–Ullmann‐type amination of aryl halides stands as one most employed reactions in modern medicinal chemistry. The work herein demonstrates potential utilizing electrochemistry to provide a complementary avenue access such critical bonds using an inexpensive nickel catalyst under mild reaction conditions. Of note is scalability, functional‐group tolerance, rapid rate, ability employ...
A simple and robust method for electrochemical alkyl C–H fluorination is presented. Using a nitrate additive, widely available fluorine source (Selectfluor), carbon-based electrodes, wide variety of activated unactivated bonds are converted into their C–F congeners. The scalability the reaction also demonstrated with 100 gram preparation fluorovaline.
The site-specific oxidation of strong C(sp3)-H bonds is uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification lead compounds truncating retrosynthetic plans, there a growing need for new reagents methods achieving such transformation both academic industrial circles. One main drawback current chemical the lack diversity with regard structure reactivity that prevents combinatorial approach rapid screening be employed. In regard,...
Abstract Simple access to aryl sulfinates from iodides and bromides is reported using an inexpensive Ni‐electrocatalytic protocol. The reaction exhibits a broad scope, uses stock solution of simple SO 2 as sulfur source, can be scaled up in batch recycle flow settings. limitations this are clearly shown put into context by benchmarking with state‐of‐the‐art Pd‐based methods.
Chiral aminoalcohols are omnipresent in bioactive compounds. Conventional strategies to access this motif involve multiple-step reactions install the requisite functionalities stereoselectively using conventional polar bond analysis. This study reveals that a simple chiral oxazolidine-based carboxylic acid can be readily transformed substituted with high stereochemical control by Ni-electrocatalytic decarboxylative arylation. general, robust, and scalable coupling used synthesize variety of...