Nickel-Catalyzed Modular Four-Component 1,4-Alkylcarbonylation of 1,3-Enynes to Tetra-Substituted CF₃–Allenyl Ketones

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2144 - 2150

Published: Jan. 25, 2024

The modular four-component carbonylation of unsaturated hydrocarbons represents an elegant strategy for the one-pot synthesis complex carbonyl compounds. However, this is currently focused on 1,2-difunctionalization olefins or alkynes, and 1,4-alkylcarbonylation 1,3-enynes remains unexplored. In study, we report a Ni-catalyzed CF3-containing under 1 atm CO, which affords tetra-substituted CF3-allenyl ketones with good yields selectivity. This protocol features mild conditions, broad substrate scope, acceptable functional group compatibility. Control experiments revealed that reactivity oxime esters (regulated by leaving groups) polarity matching are crucial success cascade. Preliminary mechanistic studies suggest acyl nickel key intermediate in transformation.

Language: Английский

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Decatungstate-photocatalyzed direct acylation of N-heterocycles with aldehydes

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(12), P. 7331 - 7336

Published: Jan. 1, 2024

A novel photocatalytic acylation strategy was developed harnessing tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst to facilitate the direct coupling of aldehydes with N-heterocycles at ambient temperature.

Language: Английский

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Tetrabutylammonium decatungstate (TBADT), a compelling and trailblazing catalyst for visible-light-induced organic photocatalysis

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(19), P. 3799 - 3842

Published: Jan. 1, 2024

Tetrabutylammonium decatungstate (TBADT) has recently emerged as an intriguing photocatalyst under visible-light or near-visible-light irradiation in a wide range of organic reactions that were previously not conceivable. Given its ability to absorb visible light and excellent effectiveness activating unactivated chemical bonds, it is promising addition traditional photocatalysts. This review covers some the contemporary developments photocatalysis enabled by TBADT catalyst 2023, with contents organized reaction type.

Language: Английский

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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

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Photoelectrochemical nickel-catalyzed carboacylation/silanoylation of alkenes with unactivated C/Si–H bonds

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(14), P. 8315 - 8322

Published: Jan. 1, 2024

A photoelectrochemical approach for the carboacylation/silanoylation of alkenes with alkanes/hydrosilanes is described. The method offers a new perspective chemists to rapidly obtain various ketones high levels structural complexity.

Language: Английский

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Photoredox-Catalyzed 1,4-Peroxidation–Sulfonylation of Enynones: A Three-Component Radical Coupling Approach for the Synthesis of Highly Functionalized Allenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 2955 - 2959

Published: April 3, 2024

An Eosin Y-catalyzed visible light-promoted 1,4-peroxidation–sulfonylation of enynones was achieved to give tetrasubstituted allenes. The photoredox catalysis Y allowed the concomitant formation peroxy and sulfonyl radicals, where preferential radical addition alkene moiety resulted in subsequent α-keto radical–sulfonyl cross couplings. developed demonstrates a regioselective 1,4-diradical strategy, opening up new possibility diradical functionalization conjugate systems.

Language: Английский

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Asymmetric imino-acylation of alkenes enabled by HAT-photo/nickel cocatalysis

Chemical Science, Journal Year: 2023, Volume and Issue: 14(23), P. 6449 - 6456

Published: Jan. 1, 2023

By merging nickel-mediated facially selective aza-Heck cyclization and radical acyl C-H activation promoted by tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst, we accomplish an asymmetric imino-acylation of oxime ester-tethered alkenes with readily available aldehydes the source, enabling synthesis highly enantioenriched pyrrolines bearing acyl-substituted stereogenic center under mild conditions. Preliminary mechanistic studies support Ni(i)/Ni(ii)/Ni(iii) catalytic sequence involving intramolecular migratory insertion tethered olefinic unit into Ni(iii)-N bond enantiodiscriminating step.

Language: Английский

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Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Molecules, Journal Year: 2023, Volume and Issue: 28(7), P. 3027 - 3027

Published: March 28, 2023

Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction functional groups. In radical difunctionalization reactions, radicals first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, ring opening. The resulting undertake following paths second functionalization: (1) couple with other groups, (2) oxidize to cations then react nucleophiles, (3) reduce anions electrophiles, (4) metal-complexes. rearrangements provide opportunity 1,3-, 1,4-, 1,5-, 1,6-, 1,7-difunctionalization products. Multiple ways initiate reaction coupling intermediate make reactions good at remote positions. These offer advantages synthetic efficiency, operation simplicity, product diversity.

Language: Английский

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Copper-Catalyzed 1,4-Trifluoromethylthio-Arylsulfonylation of 1,3-Enynes via the Insertion of Sulfur Dioxide

Organic Letters, Journal Year: 2023, Volume and Issue: 25(31), P. 5916 - 5921

Published: July 27, 2023

A copper-catalyzed trifluoromethylthio-arylsulfonylation between 1,3-enynes, AgSCF3, aryldiazonium tetrafluoroborates, and SO2 (from SOgen) is presented, which could introduce sulfone, SCF3, allene moieties into one molecule simultaneously. This strategy features mild reaction conditions, good substrate compatibility, excellent regioselectivity. The products obtained have the potential for further conversion other valuable compounds. Initial investigations mechanism suggest that it may proceed via a radical pathway. Notably, SOgen was proven as uniquely effective surrogate in this transformation.

Language: Английский

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Copper-catalyzed photoredox 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN: Facile access to α-amido allenyl nitriles

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(11), P. 109685 - 109685

Published: March 1, 2024

Language: Английский

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