A5062958149- Catalytic C–H Functionalization Methods
- Radical Photochemical Reactions
- Synthesis and Catalytic Reactions
- Catalytic Alkyne Reactions
- Immune Cell Function and Interaction
- Sulfur-Based Synthesis Techniques
- CAR-T cell therapy research
- Catalysis and Hydrodesulfurization Studies
- Asymmetric Hydrogenation and Catalysis
- Fluorine in Organic Chemistry
- Crystallization and Solubility Studies
- Protein Degradation and Inhibitors
- Cyclopropane Reaction Mechanisms
- T-cell and B-cell Immunology
- X-ray Diffraction in Crystallography
- Oxidative Organic Chemistry Reactions
Janssen (United States)
2023
Center for Child and Family Health
2014-2022
Duke University
2014-2022
The Ohio State University
2017-2020
The selective functionalization of remote C–H bonds via intramolecular hydrogen atom transfer (HAT) is transformative for organic synthesis. This radical-mediated strategy provides access to novel reactivity that complementary closed-shell pathways. As modern methods mild generation radicals are continually developed, inherent selectivity paradigms HAT mechanisms offer unparalleled opportunities developing new strategies functionalization. review outlines the history, recent advances, and...
A radical-mediated strategy for β C-H amination of alcohols has been developed. This approach employs a radical relay chaperone, which serves as traceless director that facilitates selective functionalization via 1,5-hydrogen atom transfer (HAT) and enables net incorporation ammonia at the carbon alcohols. The chaperones presented herein enable direct access to imidate radicals, allowing their first use H abstraction. streamlined protocol rapid conversion β-amino analogs (via in situ...
The first catalytic strategy to harness imidate radicals has been developed. This approach enables alkene difunctionalization of allyl alcohols by photocatalytic reduction their oxime imidates. ensuing undergo consecutive intra- and intermolecular reactions afford (i) hydroamination, (ii) aminoalkylation, or (iii) aminoarylation, via three distinct radical mechanisms. broad scope utility this method for reactivity is presented, along with comparisons other N-centered complementary,...
An iodine-catalyzed strategy for β C–H amination of alcohols is enabled by a chemo-, regio-, and stereo-selective H-atom transfer mechanism.
The kinetics of the racemization aromatic 1,3-disubstituted allenes catalyzed by gold phosphine complexes has been investigated. rate gold-catalyzed allene displayed first-order dependence on allene, and catalyst concentration kinetic analysis as a function electron-donor ability established accumulation electron density atom depletion terminal allenyl carbon atoms in rate-limiting transition state for racemization. These other observations were accord with mechanism involving rapid...
A radical cascade enables rapid, modular access to five-membered heteroarenes, including oxazoles and imidazoles, through a regio- chemo-selective β C–H bis-functionalization.
NKG2D (natural-killer group 2, member D) is a homodimeric transmembrane receptor that plays an important role in NK, γδ+, and CD8+ T cell-mediated immune responses to environmental stressors such as viral or bacterial infections oxidative stress. However, aberrant signaling has also been associated with chronic inflammatory autoimmune diseases, thought be attractive target for intervention. Here, we describe comprehensive small-molecule hit identification strategy two distinct series of...
The kinetics of the racemization 1,3-disubstituted allenes catalyzed by (IPr)AuOTf (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) has been investigated. rate gold-catalyzed allene obeyed following second-order law: krac[allene][Au]. An analysis 1-aryl-1,2-butadienes as a function electron donor ability established moderate depletion density on C1 allenyl carbon atom in rate-limiting transition state for racemization. Analysis temperature dependence 1-(p-tolyl)-1,2-butadiene...
The design of a radical relay chaperone to promote selective C–H functionalizations is described. A saccharin-based imine was found be uniquely suited effect amination alcohols via an in situ generated hemiaminal. This facilitates the mild generation N-centered while also directing its regioselective H atom transfer (HAT) β carbon alcohol. Upon halogenation, aminocyclization, and reductive cleavage, NH2 formally added vicinal development, synthetic utility, chemo-, regio-, stereoselectivity...
Abstract The mechanism of the intermolecular hydroamination 3‐methylbuta‐1,2‐diene ( 1 ) with N ‐methylaniline 2 catalyzed by (IPr)AuOTf has been studied employing a combination kinetic analysis, deuterium labelling studies, and in situ spectral analysis catalytically active mixtures. results these additional experiments are consistent for involving reversible, endergonic displacement from [(IPr)Au(NHMePh)] + 4 allene to form cationic gold π‐ C1,C2 ‐allene complex [(IPr)Au(η ‐H C=C=CMe )] I...
<b>Abstract ID 128111</b> <b>Poster Board 364</b> Natural killer group 2D (NKG2D) is a homodimeric transmembrane activating immunoreceptor whose function to detect and eliminate infected, stressed, or transformed cells that are targeted due upregulation of NKG2D ligands (NKG2DL). associates with specific adaptor molecule, the DNAX-activating protein 10kDa (DAP10), which contains signaling sequence needed for activation. has also been associated chronic inflammatory autoimmune diseases...
The mechanisms of the hydroamination enantiomerically enriched, axially chiral (R)-1-aryl-1,2-butadienes (R)-(4-C6H4R)C(H)=C=C(H)Me [R = Ph (1a), OMe (1b)] with aniline catalyzed by (IPr)AuOTf have been investigated employing a combination kinetic and stereochemical analyses in situ spectroscopy catalytically active mixtures. These experiments were consistent involving essentially irreversible displacement from [(IPr)Au(NH2Ph)]+ allene (R)-1 to form enriched gold−π-allene intermediate...