Intermolecular Redox-Neutral Carboamination of C–C Multiple Bonds Initiated by Transition-Metal-Catalyzed C–H Activation

ACS Catalysis, Год журнала: 2022, Номер 12(23), С. 14754 - 14772

Опубликована: Ноя. 18, 2022

Carboamination of readily available feedstock-like alkenes, alkynes, and allenes has proven to be an efficient powerful tool for the synthesis diverse valuable amine derivatives relevance medicinal chemistry, biochemistry, material science. Among these developed carboamination methodologies, direct use C–H activation strategy leverage process is particularly attractive due ubiquity such bonds in organic molecules. In this review, we provide overview development intermolecular across C–C π-bonds initiated by a redox-neutral nonannulative manner, with emphasis on synthetic mechanistic aspects. principle, review summarized reactions key feature involving initial metalation followed migratory insertion into terminated electrophilic amination quenching, thus, it ordered sources C- N-based functionalities further divided π-compounds.

Язык: Английский

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Dimeric Manganese‐Catalyzed Hydroalkenylation of Alkynes with a Versatile Silicon‐Based Directing Group

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(31)

Опубликована: Июнь 7, 2023

Herein, we present a manganese-catalyzed, branched-selective hydroalkenylation of terminal alkynes, under mild conditions through facile installation versatile silanol as removable directing group. With an alkenyl boronic acid the coupling partner, this reaction produces stereodefined (E,E)-1,3-dienes with high regio-, chemo- and stereoselectivity. The protocol features such room temperature air atmosphere, while maintaining excellent functional group compatibility. resulting 1,3-dienesilanol products serve building blocks, removal allows for synthesis both branched 1,3-dienes downstream reactions, well stereoselective construction linear (E,E,E)- or (E,E,Z)-1,3,5-trienes. In addition, Diels-Alder cycloaddition can smoothly selectively deliver silicon-containing pentasubstituted cyclohexene derivatives. Mechanistic investigations, in conjunction DFT calculations, suggest bimetallic synergistic activation model to account observed enhanced catalytic efficiency good regioselectivity.

Язык: Английский

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

Science Advances, Год журнала: 2025, Номер 11(3)

Опубликована: Янв. 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.

Язык: Английский

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Homogeneous Manganese-Catalyzed Hydrofunctionalizations of Alkenes and Alkynes: Catalytic and Mechanistic Tendencies

ACS Omega, Год журнала: 2022, Номер 7(42), С. 37008 - 37038

Опубликована: Окт. 11, 2022

In recent years, many manganese-based homogeneous catalytic precursors have been developed as powerful alternatives in organic synthesis. Among these, the hydrofunctionalizations of unsaturated C–C bonds correspond to outstanding ways afford compounds with more versatile functional groups, which are commonly used building blocks production fine chemicals and feedstock for industrial field. Herein, we present an account Mn-catalyzed alkenes alkynes main objective finding mechanistic tendencies that could serve a platform works come.

Язык: Английский

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Multicomponent Synthesis of 5‐Cyano‐pyrazolo[1,5‐a]pyrimidines Enabled by Aerobic Manganese Catalysis

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(6), С. 871 - 876

Опубликована: Фев. 28, 2023

An aerobic Mn(III)-catalyzed one-pot three-component synthesis of 5-cyano-pyrazolo[1,5-a]pyrimidines has been described. The synergistic combination Strecker reaction and oxidatively-induced 6π-azacyclization is the key to success this multicomponent synthesis. Differing from previous reports relied on toxic cyanating agents or multistep synthesis, mechanistically distinct protocol serves as a step-economic, regioselective functionally tolerant strategy obtain 5-cyano-pyrazolo[1,5-a]pyrimidines. As service our authors readers, journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited typeset. Technical support issues arising (other than missing files) should addressed Please note: publisher responsible content functionality any Any queries content) directed corresponding author article.

Язык: Английский

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Merging Manganese and Iminium Catalysis: Selective Hydroalkenylation of Unsaturated Aldehydes and Ketones

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(43)

Опубликована: Сен. 12, 2023

The use of synergistic catalytic strategy can usually circumvent the intrinsic limitations one system. In this communication, we disclose a cooperative catalysis manganese and iminium to realize selective hydroalkenylation unsaturated aldehydes ketones. Its success stems from LUMO activation carbonyl compounds with secondary amines as organocatalyst HOMO alkenylboronic acids Mn2 (CO)8 Br2 . This protocol exhibits several synthetic advances, e.g., simple operation, good functional group compatibility regioselectivity. theoretical calculation indicates migratory insertion followed by demetallation-isomerization process is kinetically more favorable than Michael-like nucleophilic addition. proline-derived deliver desired products in moderate enantioselectivity.

Язык: Английский

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Manganese(I)‐Catalyzed Enantioselective C(sp²)−C(sp³) Bond‐Forming for the Synthesis of Skipped Dienes with Synergistic Aminocatalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 16, 2024

Abstract Mn(I)‐catalyzed enantioselective C−C bond‐forming reactions represent a great challenge in homogeneous catalysis primarily due to limited understanding of its mechanistic principles. Herein, we have developed an interesting catalytic strategy that leverages synergistic combination dimeric manganese(I) catalyst and chiral aminocatalyst address this issue. A range conjugated dienals trienals can exclusively proceed 1,4‐hydroalkenylation by using readily available aromatic aliphatic alkenyl boronic acids as coupling partners, producing rich library skipped diene aldehydes synthetically useful yields high levels enantioselectivities. Notably, downstream transformations these products not only afford concise approach construct enantioenriched trienes but also realize total synthesis analogues (−)‐Blepharocalyxin D four steps. DFT calculations suggest the is kinetically more favorable than 1,6‐hydroalkenylation.

Язык: Английский

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Selective Functionalization of Alkenes and Alkynes by Dinuclear Manganese Catalysts

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Окт. 2, 2024

ConspectusAlkenes and alkynes are fundamental building blocks in organic synthesis due to their commercial availability, bench-stability, easy preparation. Selective functionalization of alkenes is a crucial step for the value-added compounds. Precise control over these reactions allows efficient construction complex molecules with new functionalities. In recent decades, second- third-row precious transition metal catalysts (palladium, platinum, rhodium, ruthenium) have been pivotal development metal-catalyzed synthetic methodology. These metals exhibit excellent catalytic activity selectivity, enabling functionalized molecules. However, recovery reuse long challenge this field. years, exploration earth-abundant has interested both academic industrial researchers. The such systems offers promising approach overcome limitations catalysts. For example, manganese third most naturally abundant minimal toxicity biocompatibility. It exhibits good several reactions, including C-H bond functionalization, selective reduction, radical reactions. This Account outlines our progress dinuclear catalysis alkynes. We established elementary manganese(I)-catalysis transmetalation R-B(OH)

Язык: Английский

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Catalytic Strategies for the Selective Synthesis of α‐ and β‐Functionalized Amines via Hydrofunctionalization of Enamides

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(22), С. 4606 - 4617

Опубликована: Окт. 23, 2024

Abstract α ‐ and β ‐Functionalized amines are two classes of important compounds, whose structural units widely present in approved drugs. The hydrofunctionalization enamides is the most direct efficient method for constructing these types compounds. Regioselectivity focus this conversion, largely influenced by catalytic mode. Therefore, to selectively synthesize or ‐functionalized amines, progress over past decade reviewed, pathways process discussed detail. This account aims objectively evaluate effects various on regioselectivity hydrofunctionalization, provide a new perspective selection methods design selective synthesis amines.

Язык: Английский

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Mn‐Mediated Radical Cascade Cyclization of 1,6‐Enynes with Arylboronic Acids to Access Dihydrobenzo[b]fluorenones

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(24), С. 4409 - 4414

Опубликована: Дек. 1, 2022

Abstract Herein, we report the synthesis of functionalized dihydro‐benzo[ b ]fluorenones through a manganese‐mediated cascade radical cyclization β ‐alkynyl propenones [1,6‐enynes] with arylboronic acids. In present strategy, in‐situ generated aryl undergoes chemo‐selective addition followed by 5‐ exo‐trig cyclization. The reaction is emphasized high atom‐ and step‐economy construction three new C−C bonds to access dihydrobenzo[ in 68–81% yield under mild conditions. synthetic efficacy developed method evidenced C−N bonds. magnified image

Язык: Английский

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