A5075519434- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Catalytic C–H Functionalization Methods
- Catalytic Cross-Coupling Reactions
- Crystallography and molecular interactions
- Cyclopropane Reaction Mechanisms
- Synthesis and Catalytic Reactions
- Asymmetric Hydrogenation and Catalysis
- Catalytic Processes in Materials Science
- Radical Photochemical Reactions
- Oxidative Organic Chemistry Reactions
- Hemoglobin structure and function
- Heme Oxygenase-1 and Carbon Monoxide
- Synthetic Organic Chemistry Methods
- Catalytic Alkyne Reactions
- Nanomaterials for catalytic reactions
- Methemoglobinemia and Tumor Lysis Syndrome
- Asymmetric Synthesis and Catalysis
- Fluorine in Organic Chemistry
- Chemical synthesis and alkaloids
- Nanocluster Synthesis and Applications
University of York
2014-2024
University College Cork
2015
Manganese-catalyzed C-H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven-membered Mn(I) intermediate detected characterized that effective H-transfer or reductive elimination to deliver alkenylated pyridinium products, respectively. The two pathways are determined at by judicious choice of an electron-deficient 2-pyrone substrate containing 2-pyridyl directing group, which undergoes regioselective...
A regioselective Pd-mediated C–H bond arylation methodology for tryptophans, utilizing stable aryldiazonium salts, affords C2-arylated tryptophan derivatives, in several cases quantitatively. The reactions proceed air, without base, and at room temperature EtOAc. synthetic has been evaluated compared against other derivative methods using the CHEM21 green chemistry toolkit. behavior of Pd catalyst species probed preliminary mechanistic studies, which indicate that reaction is operating...
Abstract Manganese‐catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven‐membered Mn I intermediate detected characterized that effective H‐transfer or reductive elimination to deliver alkenylated pyridinium products, respectively. The two pathways are determined at by judicious choice of an electron‐deficient 2‐pyrone substrate containing 2‐pyridyl directing group, which undergoes regioselective...
The ability of carboxylate groups to promote the direct functionalization C–H bonds in organic compounds is unquestionably one most important discoveries modern chemical synthesis. Extensive computational studies have indicated that this process proceeds through deprotonation a metal-coordinated bond by basic carboxylate, yet experimental validation these predicted mechanistic pathways limited and fraught with difficulty, mainly as rapid proton transfer frequently obscured ensemble measures...
Understanding complex reaction systems is critical in chemistry. While synthetic methods for selective formation of products are sought after, oftentimes it the full signature, i.e., complete profile products/side-products, that informs mechanistic rationale and accelerates discovery Here, we report a methodology using high-throughput experimentation multivariate data analysis to examine signature one most complicated chemical reactions catalyzed by palladium known literature. A model...
Insights into the factors controlling site selectivity of transition metal-catalyzed C–H bond functionalization reactions are vital to their successful implementation in synthesis complex target molecules. The introduction fluorine atoms substrates has potential deliver this selectivity. In study, we employ spectroscopic and computational methods demonstrate how "ortho-fluorine effect" influences kinetic thermodynamic control activation manganese(I)-mediated reactions. fluorinated...
NaNO3 is used in oxidative Pd-catalyzed processes as a complementary co-catalyst to common oxidants, e.g., CuII salts, C-H bond activation and Wacker oxidation processes. NaNO2 (with air or O2) assist the sp3-C-H acetoxylation of substrates bearing an N-directing group. It has been proposed previously that redox couple operative. The role played by NOx anions examined this investigation. Evidence for anion interaction at PdII presented. Palladacyclic complexes containing are competent...
CuI(NHC)Br complexes (NHC = N-heterocyclic carbene) undergo a direct reaction with iodobenzene to give 2-arylated benzimidazolium products. The nature of the N-substituent on NHC ligand influences reactivity complex toward arylation. N-Benzyl or N-phenyl substituents facilitate arylation, whereas N-mesityl hinder Density functional theory calculations show that an oxidative addition/reductive elimination pathway involving CuIII species is energetically feasible. A less hindered N-benzyl...
Different ‘L<sub>n</sub>Pd(0)’ species play a role in arylcyanation processes, depending on H<sub>2</sub>O content.
A new class of carbon monoxide‐releasing molecules (CO‐RMs) are reported based on a previously known tetracarbonyl phenylpyridine manganese(I) motif. pre‐functionalized CO‐RM undergoes direct Pd‐catalysed Suzuki–Miyaura cross‐coupling with phenylboronic acid to give π‐extended three‐ring CO‐RM. Cross‐coupling conditions were modified allow coupling morpholine‐containing boronic CO‐RM, introducing drug‐like functionality. An LED system was used facilitate controlled CO‐release. Irradiation...
Direct C-H functionalization reactions have opened new avenues in catalysis, removing the need for prefunctionalization of at least one substrates. Although catalyzed by palladium complexes presence a base is generally considered to proceed CMD/AMLA-6 mechanism, recent research has shown that silver(I) salts, frequently used as bases, can function bond activators instead (or addition to) palladium(II). In this study, we examine coupling pentafluorobenzene 1 4-iodotoluene 2a (and its...
Progress towards the total synthesis of macrolide natural product anthracimycin is described. This new approach utilises an intermolecular Diels-Alder strategy followed by epimeirsation to form key
Abstract The regioselective Pd‐catalyzed cyclization of a number heterocyclic substrates without added phosphine ligands is reported.