Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Язык: Английский

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E/Z Photoisomerization of Olefins as an Emergent Strategy for the Control of Stereodivergence in Catalysis

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(8), С. 1348 - 1370

Опубликована: Март 5, 2022

Abstract The stereoselective photoisomerization of olefins via Energy Transfer (E n T) sensitization bears significant potential in the context rational design catalytic stereodivergent methodologies. Whereas approaches for controlling access to E‐ and Z ‐ isomers depend highly on nature catalyst – therefore are not easily implemented as a general strategy E T catalysis has emerged recent years an increasingly powerful tool olefin geometry control nearly perfect step‐economic fashion. Moreover, this approach presents both high functional group tolerance and, most notably, demonstrated ample multicatalytic compatibility. This feature enabled development tandem strategies, which focus Review. magnified image

Язык: Английский

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Recent Advances in the Functionalization of Terminal and Internal Alkynes

Asian Journal of Organic Chemistry, Год журнала: 2022, Номер 11(5)

Опубликована: Март 9, 2022

Abstract Alkynes are one of the most fundamental and diverse functional groups utilized in organic synthesis. Over past few years, development efficient synthetic methodologies for functionalization alkynes has been an active area research. A plethora alkyne reactions have reported literature to construct functionalized alkene scaffolds, which important building blocks many natural products, pharmaceuticals, key intermediates various transformations. In this review, we describe recent advances with emphasis on substrate scope, limitations, regioselectivity control applications these reactions. This review covers from 2016 2021.

Язык: Английский

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Chemical Communications, Год журнала: 2023, Номер 59(85), С. 12669 - 12684

Опубликована: Янв. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Язык: Английский

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Nickel‐Catalyzed Defluorinative Asymmetric Cyclization of Fluoroalkyl‐Substituted 1,6‐Enynes for the Synthesis of Seletracetam

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 23, 2022

Abstract The introduction of fluorine‐containing groups into organic molecules can significantly affect their physical and chemical properties has long been used as an effective strategy for drug discovery development. Consequently, the development catalytic asymmetric methods synthesis heterocycles is highly desirable sought after. Herein, we describe a nickel‐catalyzed defluorinative cyclization fluoroalkyl‐substituted 1,6‐enynes, providing expedient access to synthetically attractive 4‐fluorovinyl‐substituted 2‐pyrrolidones in good yields with remarkable high levels chemo‐, regio‐, enantioselectivities (90–99 % ee,>35 examples). This protocol features readily available starting materials excellent functional group compatibility, exhibits complementary regioselectivity. utility this was demonstrated enantioselective antiepileptic Seletracetam.

Язык: Английский

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Photoinduced difunctionalization with bifunctional reagents containing N-heteroaryl moieties

Science China Chemistry, Год журнала: 2023, Номер 66(6), С. 1688 - 1700

Опубликована: Май 10, 2023

Язык: Английский

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Nickel-catalyzed switchable arylative/endo-cyclization of 1,6-enynes

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

Опубликована: Апрель 4, 2024

Abstract Carbo- and heterocycles are frequently used as crucial scaffolds in natural products, fine chemicals, biologically pharmaceutically active compounds. Transition-metal-catalyzed cyclization of 1,6-enynes has emerged a powerful strategy for constructing functionalized carbo- heterocycles. Despite significant progress, the regioselectivity alkyne functionalization is entirely substrate-dependent. And only exo -cyclization/cross-coupling products can be obtained, while endo -selective cyclization/cross-coupling remains elusive still poses formidable challenge. In this study, we disclose nickel-catalyzed switchable arylation/cyclization which nature ligand dictates arylation, electrophilic trapping reagents determine selectivity mode. Specifically, using commercially available 1,10-phenanthroline facilitates trans -arylation/cyclization to obtain seven-membered ring 2-naphthyl-substituted bisbox promotes cis access six-membered products. Diastereoselective cyclizations have also been developed synthesis enantioenriched piperidines azepanes, core structural elements pharmaceuticals possessing important biological activities. Furthermore, experimental density functional theory studies reveal that arylation process controlled by steric hindrance ligand; reaction mechanism involves -cyclization followed Dowd-Beckwith-type expansion form

Язык: Английский

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Gold‐Catalyzed Arylative Cope Rearrangement

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Май 21, 2024

Cope rearrangements have garnered significant attention owing to their ability undergo structural reorganization in stereoselective manner. While substantial advances been achieved over decades, these remained applicable exclusively parent 1,5-hexadienes. Herein, we disclose the gold-catalyzed arylative rearrangement of 1,6-heptadienes via a cyclization-induced [3,3]-rearrangement employing ligand-enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross-over experiment, HRMS analysis,

Язык: Английский

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Photocatalytic Reductive Functionalization of Aryl Alkynes via Alkyne Radical Anions

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9283 - 9293

Опубликована: Июнь 4, 2024

The direct reductive functionalization of alkynes under mild conditions presents a promising yet challenging avenue for accessing value-added molecules. Alkyne radical anions represent distinct class reactive intermediates characterized by both charge and an unpaired electron, thus holding great potential facilitating diverse bond formations, particularly in alkyne functionalization. However, the synthetic utility is limited, primarily due to difficulty their generation formation highly unstable vinyl intermediates. In this study, we accomplished from aryl feedstocks via single electron transfer (SET) reduction with photogenerated CO2 anion (CO2•–), enabling hydroalkylation, arylalkenylation, hydrocarboxylation alkynes. Our photocatalytic strategy features metal-free catalysis, reaction conditions, employment traceless reductant, good functional group compatibility, step- atom-economy, high regioselectivity. This study not only paves way leveraging underexplored but also catalyzes ongoing exploration bifunctional CO2•– species chemistry.

Язык: Английский

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Energy-Transfer-Enabled Radical Acylation Using Free Alkyl Boronic Acids through Photo and NHC Dual Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3181 - 3190

Опубликована: Фев. 14, 2024

Cross-coupling reactions have been well received as one of the most popular protocols for ketone synthesis. As an important coupling partner, bench-stable and commercially available alkyl boronic acids are widely used in transition metal catalysis, but they rarely utilized radical precursors acylative reactions. Herein, we reported energy-transfer-enabled acylation using free via NHC/photo dual catalysis. This protocol could efficiently promote Suzuki-type cross-coupling between acyl imidazoles multicomponent alkylacylations alkenes, thus producing various ketones with structural diversity. Additionally, products can readily transform into a large number structurally interesting fine chemicals. Preliminary mechanistic studies shed light on unique reaction mechanism.

Язык: Английский

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