First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13238 - 13341

Published: Oct. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Language: Английский

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Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(11), P. 4386 - 4464

Published: Jan. 1, 2022

The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in Earth's crust, emerged as one leading competitors. Accordingly, a large number molecularly-defined Mn-complexes been synthesized employed for hydrogenation, dehydrogenation, hydroelementation reactions. regard, catalyst design is based three pillars, namely, metal-ligand bifunctionality, ligand hemilability, redox activity. Indeed, developed catalysts not only differ chelating atoms they possess but also working principles, thereby different turnover numbers product molecules. Hence, critical assessment molecularly defined manganese terms atoms, reaction conditions, mechanistic pathway, significant. Herein, we analyze complexes catalytic activity, versatility allow multiple transformations routes convert substrates target This article will be helpful get significant insight into design, aiding design.

Language: Английский

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The transition metal-catalysed hydroboration reaction

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(21), P. 8877 - 8922

Published: Jan. 1, 2022

This review covers the development of transition metal-catalysed hydroboration reaction, from its beginnings in 1980s to more recent developments including earth-abundant catalysts and an ever-expanding array substrates.

Language: Английский

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Catalysis with Diboron(4)/Pyridine: Application to the Broad-Scope [3 + 2] Cycloaddition of Cyclopropanes and Alkenes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(19), P. 8870 - 8882

Published: May 9, 2022

In contrast to the extensive but non-recyclable use of tetraalkoxydiboron(4) compounds as stoichiometric reagents in diverse reactions, this article reports an atom-economical reaction using a commercial diboron(4) catalyst. The key success was designing catalytic cycle for radical [3 + 2] cycloaddition involving pyridine cocatalyst generate from catalyst and reversibly mediate transfer boronyl radicals. comparison with known transition metal-based catalysts, current features not only metal-free conditions, inexpensive stable simple operation also remarkably broadened substrate scope. particular, previously unusable cyclopropyl ketones without activating group and/or alkenes 1,2-disubstitution 1,1,2-trisubstitution patterns were successfully used first time. Consequently, challenging cyclopentane various levels substitution (65 examples, 57 new products, up six substituents at all five ring atoms) readily prepared generally high excellent yield diastereoselectivity. applied concise formal synthesis anti-obesity drug building natural product-like complex bridged or spirocyclic compounds. Mechanistic experiments computational investigation support proposed relay catalysis featuring pyridine-assisted Overall, work demonstrates approach catalysts may lead development new, green, efficient metal-like boron-catalyzed organic reactions.

Language: Английский

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Self-Cascade Nanoenzyme of Cupric Oxide Nanoparticles (CuO NPs) Induced in Situ Catalysis Formation of Polyelectrolyte as Template for the Synthesis of Near-Infrared Fluorescent Silver Nanoclusters and the Application in Glutathione Detection and Bioimaging

Analytical Chemistry, Journal Year: 2022, Volume and Issue: 94(42), P. 14642 - 14651

Published: Oct. 11, 2022

In this work, near-infrared fluorescent silver nanoclusters (Ag NCs) were prepared based on the in situ formed poly methacrylic acid (PMAA) as template and stabilizer, which is synthesized by (MAA) hydroxyl radical (·OH) that generated cascade nanoenzyme reaction of cupric oxide nanoparticles (CuO NPs). CuO NPs possess intrinsic glutathione-like (GPx-like) peroxidase-like (POD-like) activities, can catalyze glutathione (GSH) O2 to produce hydrogen peroxide (H2O2), then transform into ·OH. The fluorescence intensity Ag NCs decreases with addition GSH, because −SH easily anchor surface, resulting PMAA leaving NCs, coeffect GSH results aggregation form larger NPs. A good linear relationship between quenching rate concentration was found range 0.01–40 μM detection limit 8.0 nM. be applied serum, well bioimaging endogenous exogenous cells high sensitivity. Moreover, normal cancer distinguished through different levels. new method for preparation biocompatible nanoprobe nanozyme tandem catalysis avoid direct usage polymers or protein templates hinder separation, providing a reliable approach synthesis, biosensing, nanoclusters.

Language: Английский

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Investigating poly-nuclear Zn(II) and Ni(II) complexes based on a formyl-appended single salamo-type ligand

Journal of Molecular Structure, Journal Year: 2023, Volume and Issue: 1288, P. 135843 - 135843

Published: May 24, 2023

Language: Английский

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Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp³)–O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4613 - 4625

Published: Feb. 20, 2023

Since C(sp3)–O bonds are a ubiquitous chemical motif in both natural and artificial organic molecules, the universal transformation of will be key technology for achieving carbon neutrality. We report herein that gold nanoparticles supported on amphoteric metal oxides, namely, ZrO2, efficiently generated alkyl radicals via homolysis unactivated bonds, which consequently promoted C(sp3)–Si bond formation to give diverse organosilicon compounds. A wide array esters ethers, either commercially available or easily synthesized from alcohols participated heterogeneous gold-catalyzed silylation by disilanes alkyl-, allyl-, benzyl-, allenyl silanes high yields. In addition, this novel reaction could applied upcycling polyesters, i.e., degradation polyesters synthesis organosilanes were realized concurrently unique catalysis nanoparticles. Mechanistic studies corroborated notion generation is involved coupling cooperation an acid–base pair ZrO2 responsible stable bonds. The reusability air tolerance catalysts as well simple, scalable, green system enabled practical

Language: Английский

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Applications of catalysis in hydroboration of imines, nitriles, and carbodiimides

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(18), P. 3675 - 3702

Published: Jan. 1, 2022

Catalytic hydroboration of imines, nitriles, and carbodiimides are reviewed as powerful tools for preparation amines.

Language: Английский

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The Rise of Manganese-Catalyzed Reduction Reactions

Synthesis, Journal Year: 2021, Volume and Issue: 54(03), P. 517 - 534

Published: Sept. 29, 2021

Abstract Recent developments in manganese-catalyzed reducing transformations—hydrosilylation, hydroboration, hydrogenation, and transfer hydrogenation—are reviewed herein. Over the past half a decade (i.e., 2016 to present), more than 115 research publications have been reported these fields. Novel organometallic compounds new reduction transformations discovered further developed. Significant challenges that had historically acted as barriers for use of manganese catalysts reactions are slowly being broken down. This review will hopefully assist developing this area, by presenting clear concise overview catalyst structures substrate published so far. 1 Introduction 2 Hydrosilylation 3 Hydroboration 4 Hydrogenation 5 Transfer 6 Conclusion Perspective

Language: Английский

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Hydroboration of Terminal Alkenes and trans‐1,2‐Diboration of Terminal Alkynes Catalyzed by a Manganese(I) Alkyl Complex

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(46), P. 24488 - 24492

Published: Aug. 26, 2021

A MnI -catalyzed hydroboration of terminal alkenes and a 1,2-diboration alkynes with pinacolborane (HBPin) is described. For alkenes, anti-Markovnikov takes place; for the reaction proceeds excellent trans-1,2-selectivity. The most active pre-catalyst bench-stable alkyl bisphosphine complex fac-[Mn(dippe)(CO)3 (CH2 CH2 CH3 )]. catalytic process initiated by migratory insertion CO ligand into Mn-alkyl bond to yield an acyl intermediate, which undergoes B-H cleavage HBPin (for alkenes) rapid C-H alkynes), forming boryl acetylide catalysts [Mn(dippe)(CO)2 (BPin)] (C≡CR)], respectively. broad variety aromatic aliphatic was efficiently selectively borylated. Mechanistic insights are provided based on experimental data DFT calculations revealing that acceptorless operating involving dihydrogen release.

Language: Английский

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