Project description:The arylation of alkyl and aromatic terminal alkynes by a dual gold/photoredox catalytic system is described. Using aryldiazonium salts as readily available aryl sources, a range of diversely-functionalized arylalkynes could be synthesized under mild, base-free reaction conditions using visible light from simple household sources or even sunlight. This process, which exhibits a broad scope and functional group tolerance, expands the range of transformations amenable to dual gold/photoredox catalysis to those involving C-H bond functionalization and demonstrates the potential of this concept to access AuI/AuIII redox chemistry under mild, redox-neutral conditions.
Project description:Coumarin-functionalized cellulose sheets were chemically modified using a visible light catalyzed "Photo-Meerwein" arylation. Use of a photomask to pattern the surface resulted in directly visible images.
Project description:Irradiation of mixtures of title diazonium salts and heteroarenes with green light (510 nm) in the presence of eosin Y disodium salt (EY-Na2) as a photocatalyst furnished the corresponding arylation products in 8-63% yields. The proposed photocatalytic cycle is analogous to that proposed previously for closely related photoredox C-H arylations with aryl diazonium salts as aryl radical sources. This method has a broad substrate scope and represents a metal-free alternative for the synthesis of 3-heteroaryl-substituted 4H-quinolizin-4-ones and azino- and azolo-fused pyrimidones with a bridgehead nitrogen atom.
Project description:A photocatalytic method for the oxyamination of alkenes using simple nucleophilic nitrogen atom sources in place of prefunctionalized electrophilic nitrogen atom donors is reported. Copper(II) is an inexpensive, practical, and uniquely effective terminal oxidant for this process. In contrast to oxygen, peroxides, and similar oxidants commonly utilized in non-photochemical oxidative methods, the use of copper(II) as a terminal oxidant in photoredox reactions avoids the formation of reactive heteroatom-centered radical intermediates that can be incompatible with electron-rich functional groups. As a demonstration of the generality of this concept, it has been shown that diamination and deoxygenation reactions can also be accomplished using similar photooxidative conditions.
Project description:An alkyl-alkyl cross-coupling of Katritzky alkylpyridinium salts and organoboranes, formed in situ via hydroboration of alkenes, has been developed. This method utilizes the abundance of both alkyl amine precursors and alkenes to form C(sp3)-C(sp3) bonds. This strategy is also effective with alkynes, enabling a C(sp3)-C(sp2) cross-coupling. Under these mild conditions, a broad range of functional groups, including protic groups, is tolerated. As seen with previous alkylpyridinium cross-couplings, mechanistic studies support an alkyl radical intermediate.
Project description:Despite the significant progress, C-H arylation with aryldiazonium salts is a major challenge because of the faster rate of oxidative addition compared to the C-H insertion, leading to a deleterious homocoupling product. Recently, this limitation has been overcome by merging a photoredox catalyst with transition-metal catalysts which proceeds through a distinct single electron-transfer mechanism. However, we have observed that the photoredox catalyst is not necessary for the C-H arylation of aniline rather chemical reactivity can be controlled by tuning the electronic nature of the substrate. We report, herein, a palladium-catalyzed C-H arylation of aniline carbamates with aryldiazonium salts under external oxidant, acid, base free conditions at room temperature. Mechanistic studies suggest that the present reaction proceeds through a directed electrophilic metalation pathway which is the slowest step. However, the oxidative addition may take place through either ionic (2e-) or radical (1e-) pathway to generate hypervalent Pd(IV) or Pd(III) intermediate, respectively. A facile reductive elimination from the hypervalent palladium complex furnishes the C-H arylation product under mild conditions. The carbamate directing group is easily removed from the product to obtain the corresponding ortho-arylated aniline, which is a precursor for plethora of carbazole alkaloids and other biologically active molecules. The reaction is scaled-up to gram scale to furnish the desired product in comparable yields. Finally, we have applied this C-H arylation methodology for the synthesis of series of carbazole alkaloids such as clausine V, clauszoline K, O-methoxymahanine, and O-methylmurrayamine-D.
Project description:In addition to the significance of photocatalytic hydrogen evolution, the utilization of the in situ generated H/D (deuterium) active species from water splitting for artificial photosynthesis of high value-added chemicals is very attractive and promising. Herein, photocatalytic water splitting technology is utilized to generate D-active species (i.e., Dad) that can be stabilized on anchored 2nd metal catalyst and are readily for tandem controllable deuterations of carbon-carbon multibonds to produce high value-added D-labeled chemicals/pharmaceuticals. A highly crystalline K cations intercalated polymeric carbon nitride (KPCN), rationally designed, and fabricated by a solid-template induced growth, is served as an ultraefficient photocatalyst, which shows a greater than 18-fold enhancement in the photocatalytic hydrogen evolution over the bulk PCN. The photocatalytic in situ generated D-species by superior KPCN are utilized for selective deuteration of a variety of alkenes and alkynes by anchored 2nd catalyst, Pd nanoparticles, to produce the corresponding D-labeled chemicals and pharmaceuticals with high yields and D-incorporation. This work highlights the great potential of developing photocatalytic water splitting technology for artificial photosynthesis of value-added chemicals instead of H2 evolution.
Project description:We present a computational mechanistic study on the copper(III)-catalysed carboarylation-ring closure reactions leading to the formation of functionalised heterocycles. We have performed DFT calculations along selected routes and compared their free energy profiles. The calculations considered two viable options for the underlying mechanism which differ in the order of the oxazoline ring formation and the aryl transfer steps. In our model transformation, it was found that the reaction generally features the aryl transfer-ring closing sequence and this sequence shows very limited sensitivity to the variation of the substituent of the reactants. On the basis of the mechanism the origin of the stereoselectivity is ascribed to the interaction of the Cu ion with the oxazoline oxygen driving the ring-closure step selectively.
Project description:Surface grafting from diazonium solutions triggered by localized surface plasmon has been investigated. An organic layer that is 20-30 nm thick is easily grafted onto gold nanoparticles (AuNPs) by visible-light illumination in a few minutes without any reducing agent or molecular photocatalyst. Grafting depends on the wavelength and polarization of the incident light. As a consequence, the orientation of the growth of the layer deposited on the AuNPs can be controlled by polarized light. Grafting is also highly enhanced between adjacent AuNPs or at the corners of triangular AuNPs, that is, in plasmonic hot spots. These results clearly demonstrate plasmon enhancement and strongly suggest that the transfer of hot electrons from the excited plasmonic NPs to the diazonium is the main mechanism. They also confirm that localized surface plasmon resonance can induce nanolocalized electrochemical reactions, thus contributing to the field of "plasmonic electrochemistry".
Project description:Salts of the diazonium coupling agent p-phenylenebis(diazonium) form diazonium-terminated conjugated thin films on a variety of conductive and nonconductive surfaces by spontaneous reaction of the coupling agent with the surface. The resulting diazonium-bearing surface can be reacted with various organic and inorganic nucleophiles to form a functionalized surface. These surfaces have been characterized with voltammetry, XPS, infrared and Raman spectroscopy, and atomic force microscopy. Substrates that can be conveniently and quickly modified with this process include ordinary glass, gold, and an intact, fully assembled commercial screen-printed carbon electrode. The scope and convenience of this process make it promising for practical surface modification.