A5070646877- Catalytic C–H Functionalization Methods
- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Catalytic Cross-Coupling Reactions
- Radical Photochemical Reactions
- Fluorine in Organic Chemistry
- Asymmetric Hydrogenation and Catalysis
- Cyclopropane Reaction Mechanisms
- Asymmetric Synthesis and Catalysis
- Inorganic Fluorides and Related Compounds
- Chemical Reactions and Isotopes
- Synthesis and Catalytic Reactions
- Catalytic Alkyne Reactions
- Sulfur-Based Synthesis Techniques
- Synthetic Organic Chemistry Methods
- Carbon dioxide utilization in catalysis
- Innovative Microfluidic and Catalytic Techniques Innovation
- Oxidative Organic Chemistry Reactions
- Advanced Photocatalysis Techniques
- Carbohydrate Chemistry and Synthesis
- Electrochemical Analysis and Applications
- Chemical Synthesis and Reactions
- Chemical synthesis and alkaloids
- Electrocatalysts for Energy Conversion
- Organoboron and organosilicon chemistry
University of Toronto
2021-2025
Davenport University
2022
An enantioselective consecutive cyclization/coupling process, catalyzed by palladium is reported. Stereoinduction arises from an carbopalladation, generating intermediate which promotes a nucleopalladation step. The dual cyclization sequence was compatible with variety of alkyne-tethered oxygen- and nitrogen-centered nucleophiles, alkenyl-tethered aryl iodides, to forge numerous bisheterocycles in good yields high regio- enantioselectivities.
A Pd(0)/blue light catalyzed carboiodination reaction is reported. simple, air-stable catalytic system, utilizing [Pd(allyl)Cl]2 and DPEPhos, generated a variety of iodinated hetero- carbocycles including oxindoles, dihydrobenzofurans, indolines, chromane, tetrahydronaphthalene. This protocol was tolerant sensitive functional groups free carboxylic acids, phenols, anilines, as well pyridines, while delivering products in up to 94% yield. Support for reversible C–I bond formation via single...
A BF3-catalyzed atom-economical fluorocarbamoylation reaction of alkyne-tethered carbamoyl fluorides is reported. The catalyst acts as both a fluoride source and Lewis acid activator, thereby enabling the formal insertion alkynes into strong C-F bonds through halide recycling mechanism. developed method provides access to 3-(fluoromethylene) oxindoles γ-lactams with excellent stereoselectivity, including fluorinated derivatives known protein kinase inhibitors. Experimental computational...
A nickel/blue light-catalyzed carbohalogenation reaction is reported. nickel catalyst and an inexpensive phosphine ligand promote the of aryl iodides bromides with π systems to enable construction a library halogenated heterocyclic scaffolds. Mechanistic studies provide insight regarding fundamental steps catalytic cycle, including reversible C–X bond formation via deuterium labeling EPR experiments, while preliminary enantioselective results suggest two-electron migratory insertion.
A palladium-catalyzed domino C–N coupling/Cacchi reaction is reported. Design of photoluminescent bis-heterocycles, aided by density functional theory calculations, was performed with synthetic yields up to 98%. The photophysical properties the products accessed via this strategy were part a comprehensive study that led broad emission spectra and quantum 0.59. Mechanistic experiments confirmed bromoalkynes as competent intermediates, investigation suggests pathway involving initial oxidative...
Abstract A palladium‐catalyzed strategy is presented to synthesize unsymmetrically linked heterocycles within stereoselective tetrasubstituted olefins. This reaction proposed occur via a vinyl‐Pd II intermediate capable of initiating the cyclization various alkyne‐tethered nucleophiles. Products are formed in up 96 % yield and excellent stereoselectivities obtained using low catalyst loadings. transformation was scalable 1 mmol mechanistic studies suggest syn ‐carbopalladation carbamoyl...
Transition‐metal catalysis has proven useful in facilitating carbon‐halogen (C–X) bond formation. Despite the vast number of methodologies reported to furnish these bonds, limitations have remained, warranting continued development. The recent surge metallaphotoredox‐based transformations provided a novel gateway bypass limitations. Through use photoexcited species, formation C‐X bonds arise through new mechanistic pathways, finding alternatives high reaction temperatures and stoichiometric...
A palladium-catalyzed epimerization reaction of stereogenic alkyl iodides is reported. This transformation involves use an air-stable precatalyst that efficiently epimerizes the C–I bond from exo to endo face [2.2.1] bicyclic compounds. Mechanistic experiments support stereoinversion via reversible formation generate antiproduct bearing iodide. Density functional theory studies were conducted a thermodynamically driven epimerization. Stoichiometric suggested irradiation isolable alkyl–Pd(II)...
A palladium-catalyzed domino reaction of alkene-tethered oxime esters is reported. This transformation uses an air-stable palladium precatalyst that initiates a Narasaka-Heck reaction, interrupted with Pd(II)-promoted cyclization. Through this methodology, novel class unsymmetrical alkyl-linked bis-heterocycles were synthesized in yields up to 99%. The scalable 1.0 mmol, simplified purification steps. expands the scope accessible available through reactions beyond C-H activation and direct...
The reaction of alkene-tethered trifluoroacetimidoyl chlorides with trialkyl phosphites furnishes 1-amino-2,2,2-trifluoroalkylphosphonates. products were generated in moderate to good yields, and the scalability this process was showcased. Partial hydrolysis phosphonate moiety achieved. cyclization is proposed occur via formation an imidoyl intermediate that becomes susceptible nucleophilic attack at nitrogen through strong electron-withdrawing groups carbon.
Abstract An enantioselective consecutive cyclization/coupling process, catalyzed by palladium is reported. Stereoinduction arises from an carbopalladation, generating intermediate which promotes a nucleopalladation step. The dual cyclization sequence was compatible with variety of alkyne‐tethered oxygen‐ and nitrogen‐centered nucleophiles, alkenyl‐tethered aryl iodides, to forge numerous bisheterocycles in good yields high regio‐ enantioselectivities.
Abstract Base metal catalyzed C–H activation represents a highly atom economic method to access functionalized molecules. This Account will focus on Ni-catalyzed of sp3-hybridized carbon atoms with particular mechanism, recent applications, challenges, and outlook in this area. primarily mechanistic work from 2017–2023.1 Metal Activation 2 Nickel-Catalyzed sp3 3 Differences between Ni Pd 4 Mechanistic Considerations 5 Elementary Steps 6 Directed 7 Choice Directing Group 8 Primary 9 Secondary...
Abstract A base-mediated cyclization to synthesize 2-bromobenzoheterocycles is reported. This transformation was demonstrated with 16 examples access a broad range of brominated benzoheterocycles. Mechanistic studies support the reaction proceeds through bromoalkyne, and revealed an exchangeable proton at C3 indole products.
Key words copper catalysis - C–H Functionalization enantioselectivity
Key words copper - radical coupling enantioselectivity sulfur
Key words palladium - Heck coupling plycosides stereoselectivity
Key words copper - dehydrogenation phenols anilines heterocycles
Key words iridium catalysis - atroposelectivity C–H functionalization regioselectivity
Key words palladium catalysis - coupling polyarenes carbenes
Key words copper catalysis - hydroboration isosteres allenes
Key words electrochemistry - microfluidics asymmetric catalysis coupling