Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands DOI Creative Commons
Jianghao Zhang, Wenda Hu, Binbin Qian

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 4, 2023

Abstract Noble metals have been extensively employed in a variety of hydrotreating catalyst systems for their featured functionality hydrogen activation but may also bring side reactions such as undesired deep hydrogenation. It is crucial to develop viable approach selectively inhibit while preserving beneficial functionalities. Herein, we present modifying Pd with alkenyl-type ligands that forms homogeneous-like Pd-alkene metallacycle structure on the heterogeneous achieve selective hydrogenolysis and Particularly, doped carbon ligand Pd-Fe demonstrated donate electrons Pd, creating an electron-rich environment elongates distance weakens electronic interaction between unsaturated C reactants/products control hydrogenation chemistry. Moreover, high H 2 capability maintained over activated transferred Fe facilitate C-O bond cleavage or directly participate reaction Pd. The modified displays comparable rate much higher selectivity (>90%) than bare (<50%) diphenyl ether (DPE, modelling strongest linkage lignin) enhanced ethene acetylene This work sheds light controlled synthesis catalysts via mimicking homogeneous analogues.

Language: Английский

Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control DOI
Chetan C. Chintawar, Amit Kumar Yadav, Anil Kumar

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(14), P. 8478 - 8558

Published: Feb. 8, 2021

The catalyst-directed divergent synthesis, commonly termed as "divergent catalysis", has emerged a promising technique it allows chartering of structurally distinct products from common substrates simply by modulating the catalyst system. In this regard, gold complexes powerful catalysts they offer unique reactivity profiles compared to various other transition metal catalysts, primarily due their salient electronic and geometrical features. Owing tunable soft π-acidic nature, not only evolved superior contenders for catalyzing reactions alkynes, alkenes, allenes but also, more intriguingly, have been found provide reaction pathways over π-acid such Ag, Pt, Pd, Rh, Cu, In, Sc, Hg, Zn, etc. recent past witnessed renaissance in examples wherein, choosing or fine-tuning ligands, counteranions oxidation states itself, complete switch was observed. However, reviews documenting are sporadic; result, most reports kind remained scattered literature, thereby hampering further development burgeoning field. By conceptualizing idea "Divergent Gold Catalysis (DGC)", review aims consolidate all unified approach necessary pave way advancement exciting area. Based on factors governing divergence product formation, an explicit classification DGC provided. To gain fundamental understanding observed reactivities selectivities, is accompanied mechanistic insights at appropriate places.

Language: Английский

Citations

252
Toward Totally Defined Nanocatalysis: Deep Learning Reveals the Extraordinary Activity of Single Pd/C Particles DOI
Dmitry B. Eremin, Alexey S. Galushko, Daniil A. Boiko

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(13), P. 6071 - 6079

Published: March 23, 2022

Homogeneous catalysis is typically considered "well-defined" from the standpoint of catalyst structure unambiguity. In contrast, heterogeneous nanocatalysis often falls into realm "poorly defined" systems. Supported catalysts are difficult to characterize due their heterogeneity, variety morphologies, and large size at nanoscale. Furthermore, an assortment active metal nanoparticles examined on support negligible compared those in bulk used. To solve these challenges, we studied individual particles supported catalyst. We made a significant step forward fully particles. Combining nanomanipulation technique inside field-emission scanning electron microscope with neural network analysis selected unexpectedly revealed important aspects activity for widespread commercially Pd/C catalysts. The proposed approach unleashed unprecedented turnover number 109 attributed palladium nanoglobular carbon particle. Offered present study Totally Defined Catalysis concept that has tremendous potential mechanistic research development high-performance

Language: Английский

Citations

156
The interplay of carbophilic activation and Au(i)/Au(iii) catalysis: an emerging technique for 1,2-difunctionalization of C–C multiple bonds DOI
Vivek W. Bhoyare, Akash G. Tathe, Avishek Das

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(18), P. 10422 - 10450

Published: Jan. 1, 2021

This review highlights a decade-long journey of Au-catalyzed 1,2-difunctionalization reactions C–C multiple bonds that have been realized due to the productive integration Au( i )/Au( iii )catalysis with unique π-activation mode gold complexes.

Language: Английский

Citations

151
Photodynamic therapy: Innovative approaches for antibacterial and anticancer treatments DOI Creative Commons

Markéta Kolaříková,

Barbora Hošíková, Hanna Dilenko

et al.

Medicinal Research Reviews, Journal Year: 2023, Volume and Issue: 43(4), P. 717 - 774

Published: Feb. 9, 2023

Abstract Photodynamic therapy is an alternative treatment mainly for cancer but also bacterial infections. This dates back to 1900 when a German medical school graduate Oscar Raab found photodynamic effect while doing research his doctoral dissertation with Professor Hermann von Tappeiner. Unexpectedly, revealed that the toxicity of acridine on paramecium depends intensity light in laboratory. therefore based administration photosensitizer subsequent irradiation within absorption maxima this substance followed by reactive oxygen species formation and finally cell death. Although not novelty, there endeavor various modifications therapy. For example, selectivity efficiency photosensitizer, as well types sources are still being modified improve final results The main aim review summarize anticancer antibacterial modifications, namely compounds, approaches, techniques, enhance effectiveness

Language: Английский

Citations

136
Optimizing Catalyst and Reaction Conditions in Gold(I) Catalysis–Ligand Development DOI
Alba Collado, David J. Nelson, Steven P. Nolan

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(14), P. 8559 - 8612

Published: July 14, 2021

This review considers phosphine and N-heterocyclic carbene complexes of gold(I) that are used as (pre)catalysts for a range reactions in organic synthesis. These divided according to the structure ligand, with narrative focusing on studies offer quantitative comparison between ligands readily available or widely existing systems.

Language: Английский

Citations

125
Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands DOI
Chetan C. Chintawar, Vivek W. Bhoyare, Manoj V. Mane

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7089 - 7095

Published: April 18, 2022

Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential this concept has been demonstrated development 1,2-oxyarylation and 1,2-aminoarylation alkenes which provided direct access to medicinally relevant 3-oxy- 3-aminochromans (up 88% yield 99% ee). DFT studies were carried out unravel enantiodetermining step, revealed that stronger trans influence phosphorus allows selective positioning substrate in C2-symmetric environment present around nitrogen, imparting high level enantioselectivity.

Language: Английский

Citations

91
Electrochemical gold-catalysed biocompatible C(sp2)–C(sp) coupling DOI
Hao Liang,

Yilitabaier Julaiti,

Chuan‐Gang Zhao

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(4), P. 338 - 347

Published: Jan. 12, 2023

Language: Английский

Citations

46
Consolidation of the Oxidant‐Free Au(I)/Au(III) Catalysis Enabled by the Hemilabile Ligand Strategy DOI Creative Commons
Pau Font, Hugo Valdés, Xavi Ribas

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 30, 2024

Abstract In this minireview we survey the challenges and strategies in gold redox catalysis. Gold's reluctance to oxidative addition reactions due its high potential limits applicability. Initial attempts overcome problem focused on use of sacrificial external oxidants stoichiometric amounts bring Au(I) compounds Au(III) reactive species. Recently, innovative approaches employing hemilabile ligands, which are capable coordinating stabilizing square‐planar intermediates, thus facilitating steps enabling oxidant‐free Notable examples include (P^N) bidendate MeDalphos ligand achieve various cross‐coupling via Au(I)/Au(III). Importantly, ligand‐enabled catalysis allows merging with π‐activation, such as oxy‐ aminoarylation alkenols alkenamines using organohalides, expanding gold‘s versatility C−C C‐heteroatom bond formations unprecedented cyclizations. Moreover, recent advancements enantioselective chiral ligands also surveyed. Strikingly, versatile bidentate (C^N) competitors have appeared recently, by designing scaffolds where phosphine groups substituted N‐heterocyclic or mesoionic carbenes. Overall, these highlight evolving landscape tremendous a broad scope transformations.

Language: Английский

Citations

22
Arylgold nanoclusters: Phenyl-stabilized Au 44 with thermal-controlled NIR single/dual-channel phosphorescence DOI Creative Commons

Wei‐Dan Si,

Chengkai Zhang, Meng Zhou

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(7)

Published: Feb. 14, 2024

Arylation of gold holds paramount importance in the domain organometallic chemistry; however, exploration arylgold nanoclusters remains its infancy primarily due to synthetic challenge. Here, we present a facile and effective arylation strategy directly synthesize two (

Language: Английский

Citations

21
Gold-Catalyzed 1,2-Aminoarylation of Alkenes with External Amines DOI
Akash G. Tathe,

Urvashi Urvashi,

Amit Kumar Yadav

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(8), P. 4576 - 4582

Published: March 31, 2021

Reported herein is the gold-catalyzed 1,2-aminoarylation of alkenes that engages external amine as a coupling partner. Careful optimization studies revealed significant role concentration base to achieve highly chemoselective access aminoarylation products over potential C–N cross-coupled products. Overcoming all limitations, current strategy provided straightforward medicinally relevant 3-aminochroman, 2-aminotetrahydronaphthalene, and 2-aminoindane derivatives.

Language: Английский

Citations

72