Enantioselective Synthesis of N−N Biaryl Atropisomers through Iridium(I)‐Catalyzed C−H Alkylation with Acrylates

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: May 4, 2023

Abstract Enantioselective synthesis of N−N biaryl atropisomers is an emerging area but remains underexplored. The development efficient in great demand. Herein, the construction through iridium‐catalyzed asymmetric C−H alkylation reported for first time. In presence readily available Ir precursor and Xyl‐BINAP, a variety axially chiral molecules based on indole‐pyrrole skeleton were obtained good yields (up to 98 %) with excellent enantioselectivity 99 % ee). addition, bispyrrole could also be synthesized enantioselectivity. This method features perfect atom economy, wide substrate scope, multifunctionalized products allowing diverse transformations.

Language: Английский

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P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 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.

Language: Английский

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Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines

Science Advances, Journal Year: 2025, Volume and Issue: 11(3)

Published: Jan. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Language: Английский

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Catalytic Synthesis of β‐(Hetero)arylethylamines: Modern Strategies and Advances

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 21, 2023

Abstract β‐(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum biological properties, making them prime candidates for drug discovery. Conventional methods preparation often require engineered substrates that limit the flexibility synthetic routes and diversity compounds can be accessed. Consequently, provide rapid versatile access those scaffolds remain limited. To overcome these challenges, chemists have designed innovative modular strategies β‐(hetero)arylethylamine motif, paving way more extensive use future pharmaceuticals. This review outlines recent progresses synthesis (hetero)arylethylamines emphasizes how innovations enabled new levels molecular complexity, selectivity, practicality.

Language: Английский

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A General Amino–(Hetero)arylation of Simple Olefins with (Hetero)aryl Sulfonamides Enabled by an N-Triazinyl Group

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2139 - 2149

Published: Jan. 22, 2025

(Hetero)arylethylamines are privileged substructures in pharmaceuticals, agrochemicals, and other bioactive compounds. In principle, the amino–(hetero)arylation of olefins represents an ideal strategy for rapid preparation these pharmacophores, which could accelerate discovery valuable new products. Established methods, however, do not accommodate several important classes (hetero)aromatic structures, precludes access to appreciable range molecular architectures. To address limitations, we have developed a radical-mediated reaction that adds amino (hetero)aryl groups from simple stable sulfonamide across alkene. The identification readily available triazine as original N-protecting group was critical development this transformation. features good regio- stereoselectivity succeeds with medicinally unproductive alternate protocols. Lastly, highlighted advances by synthesizing TMP269, class IIa histone deacetylase inhibitor would otherwise be challenging prepare olefin amino–arylation.

Language: Английский

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Hydrogen Bond-Mediated Transition Metal-Free Alcoholysis of Primary Amides to Access Esters

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

An efficient hydrogen bond-mediated alcoholysis of primary amides was disclosed using diethyl phosphonate (DEP) as a catalyst. In this process, wide range and alcohols were tested smoothly transformed to corresponding esters in moderate good yields. This novel strategy features transition metal-free, broad substrate scope one-pot pathway. addition, the reaction showed highly chemoselective o/alcoholic o-acylation mercapto/phenolic alcohols.

Language: Английский

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Recent Progress in Metal-Catalyzed Asymmetric Hydroarylation of Internal Alkenes Through C—H Cleavage

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 546 - 546

Published: Jan. 1, 2025

Language: Английский

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Ir-Catalyzed Regio- and Enantioselective C–H Addition to 1,1-Disubstituted Alkenes Enabled by the Directing Group: Construction of Acyclic Quaternary Stereocenters

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8733 - 8739

Published: May 8, 2025

Language: Английский

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Amide-Directed, Rhodium-Catalyzed Regio- and Enantioselective Hydroacylation of Internal Alkenes with Unfunctionalized Aldehydes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 723 - 732

Published: Dec. 20, 2023

Despite the current progress achieved in asymmetric hydroacylations, highly enantioselective catalytic addition of unfunctionalized aldehydes to internal alkenes remains an unsolved challenge. Here, using a coordination-assisted strategy, we developed rhodium-catalyzed regio- and such as enamides β,γ-unsaturated amides. Valuable α-amino ketones 1,4-dicarbonyl compounds were directly obtained with high enantioselectivity from readily available materials.

Language: Английский

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Earth‐Abundant Recyclable Magnetic Iron Oxide Nanoparticles for Green‐light Mediated C−H Arylation in Heterogeneous Phase

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(44)

Published: May 24, 2024

A magnetically isolable iron oxide nanoparticles is introduced as an efficient heterogeneous photocatalyst for non-directed C-H arylation employing aryl diazonium salts the precursors. This first-row transition metal-based revealed versatile activities and applicable to a wide range of substrates, demonstrating brilliant efficacy superior recyclability. Detailed catalytic characterization describes physical properties redox behavior Fe-catalyst. Adequate control experiments helped establish radical-based mechanism arylation.

Language: Английский

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