Co(III)-Catalyzed Regioselective Benzannulation of Substituted Pyridones with 1,6-Diynes via Dual C-H Bond Activation

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(63), P. 8296 - 8299

Published: Jan. 1, 2024

A Co(III)-catalyzed site-selective C5 and C6 benzannulation of substituted pyridones with 1,6-diynes

Language: Английский

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Nucleophilic Substitution at Unactivated Arene C–H: Copper-Catalyzed anti-Selective Silylative Cyclization of Substituted Benzylacetylenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

A new mode of carbon-carbon bond formation via electrophilic activation a C-H has been developed in the context copper-catalyzed anti-selective silylative cyclization benzylacetylenes with silylboronates for synthesis 2-silyl-1H-indenes. The reaction proceeds high regioselectivity various substituted benzylacetylenes, and resulting products could be further functionalized. arene that undergoes acts as an electrophile release hydride under redox neutral conditions, mechanism was probed by deuterium-labeling experiments density functional theory calculations.

Language: Английский

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Construction of Rings via Metal‐Catalyzed C−H Annulation with Unsymmetrical Internal Alkynes: Selectivity and Applications

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(21)

Published: Aug. 19, 2023

Abstract Selective and concise construction of ring systems that are ubiquitous skeletons across chemistry, drugs materials, is indispensable for human life. Of note, directed C−H annulation with alkynes the expedient delivery holds great importance, featuring step‐ atom‐economy, mild conditions, broad substrate scope. However, regioselectivity issues remained when using unsymmetrical annulation. Herein, we summarized recent achievements towards solving this problem by developing directing groups, metal catalysts, versatile traceless functionality ensure overall regioselectivity, enantioselectivity, efficiency, synthetic application. We hope concept will promote further development precise functional molecules alkynes.

Language: Английский

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1,3‐Diynes as Precursors for the Synthesis of Triazene‐ and Diethylaniline‐Bearing Push‐Pull NLOphores

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(7)

Published: Feb. 16, 2024

Abstract Within the scope of this study, a total eight new NLOphores D‐π‐A‐π‐D type have been synthesized. This was achieved by applying click‐type [2+2] cycloaddition‐retroelectrocyclization reactions unsymmetrical 1,3‐diynes with well‐known electron‐deficient alkenes, TCNE, and TCNQ. Furthermore, essential insights into optical properties synthesized were obtained from comparisons four model compounds separately within study. The thermal stability assessed through gravimetric analysis (TGA). using two distinct alkenes exhibit low energy absorption bands covering most visible region λ max values ranging 466 nm to 723 nm. Theoretical studies, including time–dependent density functional theory (TD‐DFT) investigations, frontier orbital visualizations, electrostatic potential maps, utilized further investigate intramolecular charge transfer chromophores. NLO responses chromophores determined DFT calculations. It is worth noting that average polarizability first hyperpolarizability ( α (tot) =106.392–159.709×10 −24 esu; β =387.552–417.359×10 −30 esu) these calculations show significant promise compared literature data.

Language: Английский

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Recent advances in metal directed C–H amidation/amination using sulfonyl azides and phosphoryl azides

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(42), P. 8426 - 8462

Published: Jan. 1, 2023

This article reviews the recent advances in transition metal-catalyzed sulfonamidation and phosphoramidation of a variety organic compounds. It also covers fundamental concepts mechanistic aspects, including key intermediates reaction pathways.

Language: Английский

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Regioselective Cobalt(II) Catalyzed C–H Functionalization and [3 + 2] Annulation of N-Arylguanidines with 1,3-Diynes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7376 - 7393

Published: May 15, 2024

8-Quinolinyl directed

Language: Английский

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Theoretical Study on the Rhodium-Catalyzed Electrochemical C–H Phosphorylation: Insights into the Effect of Electro-oxidation on the Reaction Mechanism

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9352 - 9365

Published: June 29, 2023

The merging of transition-metal-catalyzed C–H bond activation with electro-oxidation has evolved into an appealing protocol for oxidative functionalization. Nevertheless, specific effects the process on reaction mechanism transition-metal catalysis have rarely been investigated. Herein, we present a comprehensive computational study rhodium-catalyzed electrochemical phosphorylation 2-phenylpyridine by diphenylphosphine oxide to reveal mechanistic details. three major chemical processes, i.e., activation, P–H and reductive elimination/C–P formation, were thoroughly addressed considering steps at Rh(III), Rh(IV), Rh(V) oxidation states. calculations demonstrated that prefers take place Rh(III) state, Rh(IV) elimination state. Without oxidation, total barrier occurring center is unsurmountable under experimental temperature. insights disclosed in are expected be beneficial understanding electro-oxidative

Language: Английский

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Enantioselective Reaction of Diynes and Multiynes for the Synthesis of Axially Chiral Compounds

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 13(1)

Published: Nov. 29, 2023

Abstract Diynes and multiynes have proven to versatile synthons for the synthesis of a range useful cyclic compounds, especially functionalized complicated polycyclic skeletons comprising carbocycles heterocycles. Axially chiral one most significant class compounds featuring axial chirality, are widely existed in natural products pharmaceuticals as well ligands catalysts. Over past decades, numerous synthetic protocols been established atroposelective axially compounds. However, catalytic asymmetric reaction diynes has rarely investigated there is no systematic brief up now. In this review, we summarize advances attainments construction also propose remained challenges opportunities future breakthroughs field.

Language: Английский

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Inorganic ligand‐supported copper catalysts catalyzing alkyne coupling reactions

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(21)

Published: April 3, 2024

Abstract Glaser‐coupled synthesized 1,3‐diyne can participate in the generation of conjugated polymers and is now widely used organic polymer synthesis. Currently, catalyst coupling are mostly based on complexation noble metals with complex ligands, which inevitably increases research cost storage difficulty. However, polyoxometalates (POMs), acidic redox properties, be as an excellent inorganic ligands low easy storage. In this work, we have copper 1 , (NH 4 ) [CuMo 6 O 18 (OH) ] a facile way applied them alkynes to obtain (non)symmetrical 1,3‐diynes high yields without bases, finally proposing reasonable reaction path. addition, showed good tolerance variety different groups, further demonstrating its catalytic activity. It worth mentioning that maintained structure activity after six cycles, promising potential for industrial applications. Thus, paper provides new strategy preparation (un)symmetrical diynes using Cu catalyst, also demonstrates multi‐acid organocatalytic

Language: Английский

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Cobalt-Catalyzed Deacylative Ipso-C–C Bond Functionalization: An Approach toward Indole-Acyloins and Its Photophysical Studies

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(13), P. 9187 - 9197

Published: June 21, 2024

Selective functionalization of the indole-C3–C bond with aromatic/heteroaromatic 1,2-diketones has been uncovered for first time. Cobalt catalyst was found to be an effective this unusual transformation. This ipso-C–C occurred in presence easily available weakly coordinating groups such as ketone and ester. One salient features methodology is situ generation water from hexafluoro-2-propanol which acts a reactant removal pivaloyl/ester group deacylative manner. The plausible mechanism supported by DFT calculations. Moreover, photophysical studies show potential utility indole-C3-acyloin indolo-fused carbazole, could used photovoltaic optoelectronic application.

Language: Английский

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