P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Год журнала: 2024, Номер 124(14), С. 8657 - 8739

Опубликована: Июль 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Язык: Английский

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Nanoarchitectonics of Non-Noble-Metal-Based Heterogeneous Catalysts for Transfer Hydrogenation Reactions: Detailed Insights on Different Hydrogen Sources

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4211 - 4248

Опубликована: Март 5, 2024

Catalytic transfer hydrogenation (CTH) methodology has drawn profound attention of researchers as an economical and environmentally benign alternate to conventional method. Unlike method, CTH exhibits better reaction efficiency atom economy, it makes use simple, easily accessible, low-cost hydrogen sources. Current research on reactions is oriented toward the development non-noble-metal-based catalysts due their high abundance potential large-scale applicability. In this Review, different organic transformation reactions, such nitroarenes, nitriles, alkenes, alkynes, carbonyl compounds, hydrogenolysis, reductive amination, formylation using sources have been summarized comprehensively. addition, synthesis strategies heterogeneous structure–activity relationship involving metal–support interaction, single-atom catalysis, synergistic effect are highlighted. Furthermore, optimization parameters─such temperature, time, solvents, additives─for enhancing catalytic activity selectivity product discussed in detail. This Review provides detailed insights into recent progress made with a specific focus catalyst development, sources, mechanistic exploration.

Язык: Английский

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Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations

ChemCatChem, Год журнала: 2024, Номер 16(14)

Опубликована: Март 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Язык: Английский

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Electrochemical Nickel‐Catalyzed Hydrogenation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(22)

Опубликована: Март 20, 2024

Olefin hydrogenation is one of the most important transformations in organic synthesis. Electrochemical transition metal-catalyzed an attractive approach to replace dangerous hydrogen gas with electrons and protons. However, this reaction poses major challenges due rapid evolution (HER) metal-hydride species that outcompetes alkene step, facile deposition metal catalyst at electrode stalls reaction. Here we report economical efficient strategy achieve high selectivity for reactivity over well-established HER. Using inexpensive bench-stable nickel salt as catalyst, mild features outstanding substrate generality functional group compatibility, distinct chemoselectivity. In addition, hydrodebromination alkyl aryl bromides could be realized using same system a different ligand, chemoselectivity between achieved through ligand selection. The practicability our method has been demonstrated by success large-scale synthesis catalytic amount electrolyte minimal solvent. Cyclic voltammetry kinetic studies were performed, which support Ni

Язык: Английский

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Secondary Alkylation of Arenes via the Borono–Catellani Strategy

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 17, 2025

A modular platform technology for the synthesis of α-aryl carbonyl derivatives via Borono-Catellani-type secondary alkylation arenes is presented. This practical method features a broad substrate scope regarding aryl boronic acid catechol esters, alkyl bromides, and diversified terminating reagents (e.g., olefins, alkynes, Zn(CN)2), mild reaction conditions, good functional-group tolerance. Importantly, asymmetric version based on dynamic kinetic transformation (DyKAT) has also been realized by introducing 1:1 diastereomeric mixture α-bromo carboxamides bearing an Evans chiral auxiliary as electrophiles, constantly excellent diastereoselectivities (>20:1 d.r.) are obtained. Notably, obtained products can be readily transformed into enantioenriched propionic derivatives, laying solid foundation discovery new NSAIDs. Through mechanistic studies DFT calculations, critical stereoretentive oxidative addition step revealed in this Borono-Catellani reaction, origins stereodiscrimination DyKAT well explained.

Язык: Английский

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Nickel-catalyzed asymmetric hydrogenation for the preparation of α-substituted propionic acids

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 28, 2024

Abstract Transition metal-catalyzed asymmetric hydrogenation is one of the most efficient methods for preparation chiral α-substituted propionic acids. However, research on this method, employing cleaner earth-abundant metal catalysts, still insufficient in both academic and industrial contexts. Herein, we report an nickel-catalyzed acrylic acids affording corresponding with up to 99.4% ee (enantiomeric excess) 10,000 S/C (substrate/catalyst). In particular, method can be used obtain ( R )-dihydroartemisinic acid 99.8:0.2 dr (diastereomeric ratio) 5000 S/C, which essential intermediate antimalarial drug Artemisinin. The reaction mechanism has been investigated via experiments DFT (Density Functional Theory) calculations, indicate that protonolysis C-Ni bond key intramolecular proton transfer from carboxylic group substrate, rate-determining step.

Язык: Английский

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Mild and selective synthesis of imines and N-Heterocyclic compounds via formic acid-mediated reductive coupling strategy over Nitrogen-Coordinated cobalt Single-Atom catalysts

Chemical Engineering Journal, Год журнала: 2024, Номер 493, С. 152774 - 152774

Опубликована: Июнь 7, 2024

Язык: Английский

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Earth‐Abundant Nickel‐Catalyzed Asymmetric Hydrogenation^†

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(23), С. 3135 - 3156

Опубликована: Авг. 13, 2024

Comprehensive Summary Transition metal‐catalyzed asymmetric hydrogenation is an efficient and direct synthetic method to access chiral compounds, which features simplicity, easy working‐up process, high atomic economy. It typically relies on precious transition metal catalytic systems, including ruthenium, rhodium, iridium palladium, always face the difficulties of limited resources, cost, environmental contamination. Therefore, great efforts were made apply earth‐abundant, low (non‐)toxic, environmentally friendly metals, such as iron, cobalt, nickel copper, in past decades, some considerable breakthroughs have been obtained. In this review, we mainly summarized recent research progress nickel‐catalyzed prochiral unsaturated molecules, olefins, imines ketones. And continuous development systems application them into challenging prospected future. Key Scientists has regarded important approach molecules. The first example homogeneous was developed by Knowles Horner 1968, respectively. 1971, Kagan privileged DIOP ligand for hydrogenation. Halpern Brown deep studies Rh‐catalyzed 1977, Noyori a powerful BINAP 1980. Owing Noyori's contribution field hydrogenation, they awarded Nobel Prize Chemistry 2001. 1984, Ohkubo pioneering earth‐abundant Ni‐catalyzed ethyl α‐methylcrotonate. A many scientists tremendous ligands, as, Bosnich, Kumada, Giongo, Takaya, Miyashima, Achiwa, Burk, Pflaltz, Chan, X. Zhang, Imamoto, Zhou, Genet, Sannicolo, Ding, Hoge, W. Z. Tang, these ligands owned wide addition, Fan investigation aromatic heterocyclic compounds. importance (transfer) promoted cheap researchers, Hamada, Gao, J. S. Chirik, Y.‐G. Lv, Dong, Fu, Deng, Hou, there are other that also transformation, with too space list all them.

Язык: Английский

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Stereoselective Nickel-Catalyzed Iterative 1,2-Reduction of Trisubstituted Enones to Cycloalkanols Bearing Two Contiguous Stereocenters

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Herein we first report a nickel-catalyzed asymmetric iterative 1,2-reduction of trisubstituted enones to cycloalkanols with two contiguous stereocenters in high yields excellent diastereo- and enantioselectivities (36 examples, up 98.5:1.5 er, >20:1 dr, TON = 500). The combined experimental computational mechanistic studies suggested energy changes during consecutive reduction processes provided range unique rationales that have not been disclosed hydrogenation-related studies.

Язык: Английский

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Enantioselective Synthesis of Chiral β²-Amino Phosphorus Derivatives via Nickel-Catalyzed Asymmetric Hydrogenation

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 27, 2024

Compared with chiral β3-amino phosphorus compounds, which can be easily derived from natural optically pure α-amino acids, obtaining β2-amino derivatives remains a challenge. These derivatives, cannot amino possess unique biological activities or potential catalytic activities. Herein, highly enantioselective hydrogenation for the preparation of E-β-enamido compounds is reported by using green and low-cost earth-abundant metal nickel catalyst (13 examples 99% ee). In particular, this system provides same enantiomer product E- Z-alkene substrates, E/Z-substrate mixtures provide good results (up to 96% The products diversely derivatized, exhibit as novel β2-aminophosphine ligands. Density functional theory calculations reveal that weak attractive interactions between substrate are crucial achieving perfect enantioselectivities. addition, different coordination modes Z-substrates may result in formation product.

Язык: Английский

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