A5017696327- Catalytic C–H Functionalization Methods
- Catalytic Cross-Coupling Reactions
- Asymmetric Hydrogenation and Catalysis
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Synthesis and Catalytic Reactions
- Radical Photochemical Reactions
- Fluorine in Organic Chemistry
- Inorganic Fluorides and Related Compounds
- Organic Light-Emitting Diodes Research
- Organoboron and organosilicon chemistry
- Molecular Junctions and Nanostructures
- Oxidative Organic Chemistry Reactions
- Metal-Catalyzed Oxygenation Mechanisms
- Synthetic Organic Chemistry Methods
- Luminescence and Fluorescent Materials
- Asymmetric Synthesis and Catalysis
- Advanced Battery Technologies Research
- Advancements in Battery Materials
- Covalent Organic Framework Applications
- Cyclopropane Reaction Mechanisms
- Catalytic Alkyne Reactions
- Porphyrin and Phthalocyanine Chemistry
- Advanced Battery Materials and Technologies
- Organic Electronics and Photovoltaics
Massachusetts Institute of Technology
2023-2025
Institute for Basic Science
2016-2024
Korea Advanced Institute of Science and Technology
2016-2024
Government of the Republic of Korea
2019-2021
Catalytic Materials (United States)
2017-2021
Daejeon University
2019
Quantum chemical molecular modeling has become a standard tool in organometallic chemistry. In particular, density functional theory calculations are now indispensable for investigating the mechanism of even complex reactions and deliver precise energies intermediates transition states. Because software packages have user-friendly widely available, nonexperts can produce high-quality computer models. this tutorial, we highlight nontrivial mistakes, misconceptions, misinterpretations often...
Abstract Terminal cobalt(IV)–oxo (Co IV –O) species have been implicated as key intermediates in various cobalt-mediated oxidation reactions. Herein we report the photocatalytic generation of a mononuclear non-haem [(13-TMC)Co (O)] 2+ ( 2 ) by irradiating [Co II (13-TMC)(CF 3 SO )] + 1 presence [Ru (bpy) ] , Na S O 8 and water an oxygen source. The intermediate was also obtained reacting with artificial oxidant (that is, iodosylbenzene) characterized spectroscopic techniques. In particular,...
Ullmann-type C-N coupling reactions represent an important alternative to well-established Pd-catalyzed approaches due the differing reactivity and lower cost of Cu. While design anionic Cu ligands, particularly those by Ma, has enabled various classes aryl halides alkyl amines, most methods require conditions that can limit their utility on complex substrates. Herein, we disclose development N1,N2-diarylbenzene-1,2-diamine ligands promote Cu-catalyzed amination bromides under mild...
Abstract We disclose the development of a Cu‐catalyzed C−O coupling method utilizing new N 1 , 2 ‐diarylbenzene‐1,2‐diamine ligand, L8 . Under optimized reaction conditions, structurally diverse aryl and heteroaryl bromides underwent efficient with variety alcohols at room temperature using an ‐based catalyst. Notably, ‐derived catalyst exhibited enhanced activity when compared to L4 system previously disclosed for C−N coupling, namely ability functionalize containing acidic functional...
Enantioenriched molecules bearing indole-substituted stereocenters form a class of privileged compounds in biological, medicinal, and organic chemistry. Thus, the development methods for asymmetric indole alkylation is highly valuable synthesis. Traditionally, achieving N-selectivity reactions significant challenge, since there an intrinsic preference at C3, most nucleophilic position. Furthermore, selective predictable access to either N- or C3-alkylated chiral indoles using catalyst...
We report a general and functional-group-tolerant method for the Cu-catalyzed amination of base-sensitive aryl bromides including substrates possessing acidic functional groups small five-membered heteroarenes. The results presented herein substantially expand scope C–N coupling reactions. combination L8, an anionic N1,N2-diarylbenzene-1,2-diamine ligand, along with mild base NaOTMS leads to formation stable yet reactive catalyst that resists deactivation from coordination heterocycles or...
A new transition-metal-free borylation of aryl and vinyl halides using 1,1-bis[(pinacolato)boryl]alkanes as boron sources is described. In this transformation one the groups from selectively transferred to in presence sodium tert-butoxide only activator form organoboronate esters. Under developed conditions, a broad range organohalides are borylated with excellent chemoselectivity functional group compatibility, thus offering rare example protocol. Experimental theoretical studies have been...
Dual emission featuring both thermally activated delayed fluorescence (TADF) and phosphorescence was engineered into a single metal-free molecule, phenyl(10-phenyl-10H-phenoselenazin-3-yl)methanone. Selenium incorporated the molecule increases spin-orbit coupling to facilitate TADF phosphorescence, whereas donor-acceptor units promote emission. The relative contribution of green yellow can be controlled by driving voltage devices. At low voltage, dominates electroluminescence, is major...
Described herein is the synthesis of NiII complex (tBuMe2tacn)NiII(cycloneophyl) (tBuMe2tacn = 1-tert-butyl-4,7-dimethyl-1,4,7-triazacyclononane, cycloneophyl -CH2CMe2-o-C6H4-) and its reactivity with dioxygen peroxides. The new tBuMe2tacn ligand designed to enhance oxidatively induced bond-forming high-valent Ni intermediates. Tunable chemoselectivity for Csp2-O vs Csp2-Csp3 bond formation was achieved by selecting appropriate solvent reaction conditions. Importantly, use cumene...
Abstract The utilization of redox mediators (RMs) in lithium–oxygen batteries (LOBs) has underscored their utility high overpotential during the charging process. Among currently known RMs, it is exceptionally challenging to identify those with a potential capable attenuating singlet oxygen ( 1 O 2 ) generation while resisting degradation by reactive species (ROS), such as and superoxide (O •− ). In this context, computational experimental approaches for rational molecular design have led...
Abstract The excellent contrast ratio, visibility, and advantages in producing thin light displays let organic emitting diodes change the paradigm of display industry. To improve future technologies, higher electroluminescence efficiency is needed. Herein, detailed study non-radiative decay mechanism employing density functional theory calculations carried out a simple, general strategy for design ancillary ligand formulated. It shown that steric bulk properly directed towards...
Purely organic phosphorescent emitters have been developed with the incorporation of alkyl substituents into <italic>N</italic>-phenylphenoselenazine core.
We report a mild method for the copper-catalyzed amination of aryl chlorides. Key to success was use highly sterically encumbered
The systematic investigation of chiral bidentate auxiliaries has resulted in the discovery a 2,2-dimethyl-1-(pyridin-2-yl)propan-1-amine-derived directing group that enables stereoselective palladium(ii)-catalyzed intramolecular C(sp3)-O bond formation. This new exhibited high reactivity activation methylene C(sp3)-H bonds with excellent levels stereoselectivity (a diastereomeric ratio up to 39 : 1), which allowed construction wide range oxaspirocycles. Mechanistic investigations were also...
The mechanism of the Buchwald–Hartwig amination assisted by base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is explored with density functional theory (DFT) calculations. Whereas previous study indicates that tight binding DBU to Pd(II) center could block desired catalytic pathways, recent work from Buchwald and co-workers demonstrates bulkier ligands, such as AlPhos, can overcome catalyst deactivation yield C–N-coupled product at room temperature. results show ligands sterically hinder enable...
Steric bulk has been recognized as a central design principle for ligands in the widely utilized Buchwald–Hartwig amination. This mechanistic study reveals how this steric effect manipulates reaction pathway and determines chemoselectivity.
Ruthenium(II)-catalyzed reactions of cyclic diazodicarbonyl compounds with β-ketoamides for chemo- and stereoselective construction cyclohexanone-fused γ-butenolides are described. This study represents the first example addition an enol substrate which is formed by tautomerization to electrophilic carbene center unusual cyclization through amide cleavage. The combined experimental computational studies shed light on mechanistic pathway favouring ring formation reaction instead involvement...
Copper-catalyzed stereoconvergent allylation of chiral sp3 -hybridized carbon nucleophiles with a racemic mixture acyclic secondary allylic phosphates is reported. In the presence copper-catalyst complexed BenzP* ligand, tandem coupling reaction vinyl arenes, bis(pinacolato)diboron, and provided β-chiral alkylboronates possessing (E)-alkenyl moiety through direct concomitant generation C(sp3 )-stereogenic center. A range (hetero)arenes bearing 1°, 2°, 3° alkyl phenyl α-substituents were...
Pd-catalyzed nucleophilic fluorination reactions are important methods for the synthesis of fluoroarenes and fluoroalkenes. However, these can generate a mixture regioisomeric products that often difficult to separate. While investigating cyclic vinyl triflates, we observed addition substoichiometric quantity TESCF
Transition-metal-catalyzed C–O coupling reactions of aryl halides and alcohols represent a useful alternative to classical aromatic substitution methods due their improved functional group tolerance substrate scope. Despite these benefits, many existing protocols rely on harsh reaction conditions or necessitate the use significant molar excess alcohol facilitate efficient bond formation, thereby limiting utility with complex substrates. Herein, we disclose development Cu-catalyzed method...
A pentadentate pyridinophane ligand is reported, along with a palladacycle product generated via Csp 3 –H bond activation under mild conditions.
A novel Pd<sup>II</sup> precursor activation by pivalate was discovered. Pivalate found to decarboxylate and act as a reductant, suggesting an alternative explanation for the superior performance of its use in Pd-catalyzed direct C–H arylation reactions.
<b>Enantioenriched molecules bearing indole-substituted stereocenters form a class of privileged compounds in biological, medicinal, and organic chemistry. Thus, the development methods for asymmetric indole alkylation is highly valuable synthesis. Traditionally, achieving N-selectivity reactions significant challenge, since there an intrinsic preference at C3, most nucleophilic position. Furthermore, selective predictable access to either N- C3-alkylated chiral indoles using catalyst...
Abstract We disclose the development of a Cu‐catalyzed C−O coupling method utilizing new N 1 , 2 ‐diarylbenzene‐1,2‐diamine ligand, L8 . Under optimized reaction conditions, structurally diverse aryl and heteroaryl bromides underwent efficient with variety alcohols at room temperature using an ‐based catalyst. Notably, ‐derived catalyst exhibited enhanced activity when compared to L4 system previously disclosed for C−N coupling, namely ability functionalize containing acidic functional...