#RobSelects paper of the week #ACSCatalysis: Nickel-catalyzed dehydroxylative cross-coupling of 1-substituted cyclopropanols and boronic acids via gamma-carbon-carbon activation. #catalysis https://doi.org/10.1021/acscatal.5c07422

#RobSelects paper of the week #ACSCatalysis: Accelerating automated reaction pathway exploration through the incorporation of ontological constraints and structural reasoning. #compchem https://doi.org/10.1021/acscatal.5c06298

Structural and Functional Dissection of GH161 β-Glucan Phosphorylases: Molecular Specificities and Dynamics of Catalysis of Dimeric GH-Q Enzymes In the CAZy classification of carbohydrate-active enzymes, the GH-Q clan regroups three distantly related glycoside hydrolase (GH) families: GH94, GH149, and GH161. These families contain glycoside ph...

Unlocking the secrets of GH161 enzymes! 🧬 Using cryo-EM, Moulis, Cioci, & co-workers reveal how β-glucan phosphorylases reshape during catalysis—shedding light on the molecular choreography of GH-Q clan enzymes #Biocatalysis #ACSCatalysis @cathleencrudden.bsky.social

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Temporal Resolution of In Situ TEM Limits the Characterization of Catalyst Site Dynamics In situ transmission electron microscopy (TEM) provides a means for capturing atomic-resolution micrographs under reactive environments and has been widely employed to identify active site candidates ...

In situ TEM doesn't get the full picture. Atomic-resolution imaging is powerful, but sub-nanosecond catalyst dynamics remains difficult. This #EditorsChoice #ACSCatalysis Viewpoint shows why we need more than TEM by Tibor Szilvási

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Asymmetric Diamination of the In Situ Generated Difluoroenol Species Using Azocarboxamides as an N Source The Rh2(esp)2 and Zn(II)-bisoxazoline (BOX) complex-cocatalyzed asymmetric diamination of in situ generated difluoroenol species with azocarboxamides has been disclosed. This reaction features a formal [3 + 2]-cycloaddition reaction using difluoroenol intermediate as a C2 synthon, providing an efficient and robust approach for the synthesis of difluorinated imidazolidin-2-ones in good yields with high to excellent stereoselectivity (up to 95% ee). This method offers a complementary approach for the direct assembly of chiral difluoromethylene incorporated heterocycles by introducing in situ formed difluoroenol species as a practical C2 synthon rather than using presynthesized gem-difluoroalkenes. With this protocol, further synthetic applications in fluorine chemistry could be envisioned through the strategic interception of difluoroenol via cycloaddition reactions with appropriate partners.

Check out this CF2 synthon enabled by dual Rh-Zn catalysis in #ACSCatalysis #EditorsChoice

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Cu-Catalyzed C–H Phenothiazination toward the Assembly of Cyclopeptides @pubs.acs.org @ehuzientzia.bsky.social #ACSCatalysis pubs.acs.org/doi/10.1021/...

On the Hunt for Chiral Single-Atom Catalysts Enantioselective transformations are crucial in various fields, including chemistry, biology, and materials science. Today, the selective production of enantiopure compounds is achieved through asymme...

We just published a new perspective in #ACSCatalysis (@acs.org) discussing key challenges and a roadmap for bringing enantioselectivity into the world of #SACs! Congrats to Theo and Vincenzo!

#EU_funded | @erc.europa.eu | #MSCA pubs.acs.org/doi/10.1021/...

Areti's work is featured on the Cover of #ACSCatalysis (@acs.org)!
The paper can be accessed here 👉 doi.org/10.1021/acsc...

#EUfunded

Ni-Catalyzed Cyanation of (Hetero)Aryl Electrophiles Using the Nontoxic Cyanating Reagent K4[Fe(CN)6] A Ni-catalyzed cyanation of aryl halides using potassium ferrocyanide (K4[Fe(CN)6]) as a nontoxic cyanide source has been developed. Key features of this method include the use of biphasic aqueous con...

Cool #ACSCatalysis from #BMSChemistry on Ni-catalyzed cyanation with K- ferrocyanide - a low tox CN source. Also the reaction is done in nButyl acetate - the best solvent b/c it smells amazing!

Tracking Charge Dynamics in a Silver Single-Atom Catalyst During the Light-Driven Oxidation of Benzyl Alcohol to Benzaldehyde Understanding charge transfer in light-driven processes is crucial for optimizing the efficiency and performance of a photocatalyst, as charge transfer directly influences the separation and migration of photogenerated charge carriers and determines the overall reaction rate and product formation. However, achieving this understanding remains challenging in the context of single-atom photocatalysis. This study addresses this gap and investigates an Ag-based single-atom catalyst (Ag1@CNx) in the photocatalytic oxidation of benzyl alcohol to benzaldehyde. Comprehensive characterization was conducted using a battery of diffractive, textural, spectroscopic, and microscopic methods, confirming the catalyst crystallinity, porosity, elemental composition, and atomic dispersion of silver atoms. This material displayed efficient performance in the selective oxidation of benzyl alcohol to benzaldehyde. Density functional theory calculations were used to rationalize the catalyst structure and elucidate the reaction mechanism, unveiling the role of the photogenerated holes in lowering the reaction energy barriers. Time-resolved transient spectroscopic studies were used to monitor the dynamics of photogenerated charges in the reaction, revealing the lifetimes and behaviors of excited states within the catalyst. Specifically, the introduction of silver atoms led to a significant enhancement in the excited state lifetime, which favors the hole-transfer in the presence of the benzyl alcohol. This indicated that the photoexcited carriers were effectively transferred to the reactant, thereby driving the oxidation process in the presence of oxygen. These mechanistic insights are pivotal in spectroscopically elucidating the reaction mechanism and can be practically applied to design single-atom photocatalysts more rationally, targeting materials that combine both rapid reductive quenching and efficient charge transfer to the metal.

Just out in #ACSCatalysis @acs.org! We show how isolated Ag atoms boost excited-state lifetimes & hole transfer, enhancing catalysis. Key insights for next-gen SACs for fine chemicals.👇

#EU_funded @erc.europa.eu

Want to learn more about catalytic dehydrogenative polymerization or single-atom-alloy catalysts? Check out these reviews and perspectives recently published in #ACSCatalysis! #chemsky

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This #ACSCatalysis cover features nitrogen-directed C(sp3)–H and C(sp2)–H borylation with pinacolborane (HBpin) at near-room temperature using an Ir(cod) catalyst with a spiro-fluorene-indenoindenyl (SFI) ligand [ pubs.acs.org/doi/10.1021/... ]

#RobSelects paper of the week #ACSCatalysis: Systematic framework for reconciling kinetic information extracted from cyclic voltammetry to computed Gibbs free energy profiles of catalytic reactions. #physchem https://doi.org/10.1021/acscatal.4c06976

A graphic showing a central chemical structure of a palladium-coordinated central N-alkyl piperidine which then undergoes either productive γ-C-H cleavage or decomposition via β-H elimination. DFT structures highlight how an N-Ac amino acid ligand favours the productive γ-C-H cleavage due to geometic restriction around the Pd-centre. Find this work at https://pubs.acs.org/doi/10.1021/acscatal.4c06160

Check out our new work in 3° alkylamine directed #Pd catalysed C-H activation in #ACSCatalysis. Jesus shows how an amino acid ligand favours one CMD pathways to preferentially give γ-C(sp3)-H actiavtion over β-H elimination enabling us to make some strained 4° centres.

#ChemSky 🧪⚗️

#RobSelects paper of the week #ACSCatalysis: Nickel-catalyzed activation of acylsilanes via Fischer carbene nickel complexes. #catalysis https://doi.org/10.1021/acscatal.4c06272