Coordination-driven innovations in low-energy catalytic processes: Advancing sustainability in chemical production

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 514, P. 215900 - 215900

Published: May 8, 2024

Catalysis stands as a cornerstone in chemical synthesis, pivotal advancing sustainable manufacturing pathways. The evolution from energy-intensive to catalytic processes has marked transformative shift, notably exemplified by low-energy methods. These processes, operating under milder conditions and emphasizing selectivity recyclability, represent the forefront of chemistry. This review navigates through an array reactions, highlighting their diverse applications culminating exploration recent strides within processes. For example, explores uses such enzyme mimicking, biodiesel production, carbon dioxide capture, organic synthesis. Additionally, it covers enzymatic catalysis photocatalysis for transformations, energy applications, water treatment. Notably, emphasizes capabilities single-atom (SAC) diatomic catalysts (DACs), recognizing exceptional performance catalyzing reactions at minimal activation energies while maintaining high efficiency mild conditions. By elucidating modulation electronic structure offering microelectronic perspective, aims elucidate mechanisms underlying activity SAC DACs. Emphasizing interplay between coordination chemistry principles efficacy, elucidates indispensable role complexes fortifying sustainability these spotlighting fusion with catalysis, this underscore collective influence shaping landscape production.

Language: Английский

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Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp³)/Si–H Functionalization and Hydrofunctionalization of Alkenes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8731 - 8751

Published: June 16, 2023

Electrochemically driven hydrogen atom transfer (HAT) catalysis provides a complementary approach for the transformation of redox-inactive substrates that would be inaccessible to conventional electron (ET) catalysis. Moreover, electrochemically HAT could promote organic transformations with either abstraction or donation as key step. It versatile and effective tool direct functionalization C(sp3)–H/Si–H bonds hydrofunctionalization alkenes. Despite these attractive properties, has been largely overlooked due lack understanding both catalytic mechanism how catalyst selection should occur. In this Review, we give an overview applications in The mechanistic pathways, physical properties mediators, state-of-the-art examples are described discussed.

Language: Английский

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Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

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The design of PINO-like hydrogen-atom-transfer catalysts

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(9), P. 653 - 666

Published: July 18, 2023

Language: Английский

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Pyridine N-oxides as hydrogen atom transfer reagents for site-selective photoinduced C(sp3)–H functionalization

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(5), P. 568 - 575

Published: May 2, 2024

Photoinduced C(sp3)–H functionalization through hydrogen atom transfer (HAT) processes is pivotal in organic synthesis because of the mild reaction conditions and applicability to late-stage complex molecules, such as pharmaceuticals agrochemicals. Despite promise, achieving precise site-selectivity overcoming high bond dissociation energy (BDE) unactivated aliphatic C–H bonds photoinduced reactions, HAT, are challenging. In this landscape, pyridine N-oxides have emerged potent HAT reagents due their easily tunable nature. This Perspective highlights studies showcasing potential site-selective abstraction from explores structure–activity relationship with multiple hydrocarbon substrates. Pyridine become promising environmentally friendly owing cost-effectiveness, tunability (heterogeneous) catalysis. Ongoing research on use will probably offer additional avenues for efficient selective functionalization. processes, a useful tool synthesis, but challenges remain. showcases highlighting how they can be readily tuned achieve site-selectivity.

Language: Английский

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Microwave-assisted synthesis of bioactive heterocycles: An overview

Tetrahedron, Journal Year: 2022, Volume and Issue: 126, P. 133085 - 133085

Published: Oct. 12, 2022

Language: Английский

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Asymmetric Olefin Isomerization via Photoredox Catalytic Hydrogen Atom Transfer and Enantioselective Protonation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18307 - 18315

Published: Aug. 8, 2023

Asymmetric olefin isomerization can be appreciated as an ideal synthetic approach to access valuable enantioenriched C═C-containing molecules due the excellent atom economy. Nonetheless, its occurrence usually requires a thermodynamic advantage, namely, higher stability of product substrate. It has thus led rather limited examples success. Herein, we report photoredox catalytic hydrogen transfer (HAT) and enantioselective protonation strategy for challenging asymmetric isomerization. As paradigm, by establishing dual catalyst system involving visible light photosensitizer DPZ chiral phosphoric acid, with assistance N-hydroxyimide perform HAT, wide array allylic azaarene derivatives, featuring α-tertiary carbon stereocenters β-C═C bonds, was synthesized high yields, ees, E/Z ratios starting from conjugated α-substituted alkenylazaarene E/Z-mixtures. The good compatibility assembling deuterium on using inexpensive D2O source further underscores broad applicability promising utility this strategy. Moreover, mechanistic studies have provided clear insights into challenges in terms reactivity enantioselectivity. exploration will robustly inspire development thermodynamically unfavorable isomerizations.

Language: Английский

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The Unique Role of the Second Coordination Sphere to Unlock and Control Catalysis in Nonheme Fe(II)/2-Oxoglutarate Histone Demethylase KDM2A

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(23), P. 10737 - 10755

Published: May 23, 2024

Nonheme Fe(II) and 2-oxoglutarate (2OG)-dependent histone lysine demethylases 2A (KDM2A) catalyze the demethylation of mono- or dimethylated 36 residue in H3 peptide (H3K36me1/me2), which plays a crucial role epigenetic regulation can be involved many cancers. Although overall catalytic mechanism KDMs has been studied, how KDM2 catalysis takes place contrast to other remains unknown. Understanding such differences is vital for enzyme redesign help enzyme-selective drug design. Herein, we employed molecular dynamics (MD) combined quantum mechanics/molecular mechanics (QM/MM) explore complete KDM2A, including dioxygen diffusion binding, activation, substrate oxidation. Our study demonstrates that KDM2A controlled by conformational change second coordination sphere (SCS), specifically orientation Y222, unlocks 2OG rearrangement from off-line in-line mode. The variant Y222A makes more favorable. Furthermore, reveals it size H3K36me3 prevents rearrangement, thus rendering inactivity with trimethylated lysine. Calculations show SCS long-range interacting residues stabilize HAT transition state differ those KDM4A, KDM7B, KDM6A, providing basics modulation without influencing KDMs.

Language: Английский

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NHPI-Mediated Electrochemical α-Oxygenation of Amides to Benzimides

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(5), P. 2985 - 2998

Published: Feb. 22, 2023

This report describes a mild electrochemical α-oxygenation of wide range linear and cyclic benzamides mediated by N-hydroxyphthalimide (NHPI) in an undivided cell using O2 as the oxygen source 2,4,6-trimethylpyridine perchlorate electrolyte. The radical scavenger experiment 18O labeling were carried out, which indicated involvement pathway suggested imides, respectively.

Language: Английский

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The literature of heterocyclic chemistry, part XXII, 2022

Advances in heterocyclic chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

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