Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(21), P. 16110 - 16293

Published: Sept. 16, 2022

In the present review, we discuss recent progress in field of C–Z bond formation reactions (Z = S, Se, Te) catalyzed by transition metals. Two complementary methodologies are considered─catalytic cross-coupling and catalytic addition reactions. The development advanced systems is aimed at improved catalyst efficiency, reduced loading, better cost environmental concerns, higher selectivity yields. important rise research efforts sustainability green chemistry areas critically assessed. paramount role mechanistic studies a new generation addressed, key achievements, problems, challenges summarized for this field.

Language: Английский

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Transient imine directing groups for the C–H functionalisation of aldehydes, ketones and amines: an update 2018–2020

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(37), P. 7291 - 7315

Published: Jan. 1, 2020

This review describes recent advances in C–H functionalisation using transient directing groups. Advances group design, new bond forming methodologies, regio- and stereoselective processes, mechanistic insights are discussed.

Language: Английский

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Chiral Transient Directing Groups in Transition-Metal-Catalyzed Enantioselective C–H Bond Functionalization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(21), P. 12898 - 12919

Published: Oct. 21, 2020

Transition-metal-catalyzed C–H bond functionalization has known a rapid evolution in the last years, offering modern strategies for reaching high molecular complexity step- and atom-economical way. Despite indisputable advances, selectivity issues still remain, given ubiquity of bonds on molecules; thus, several approaches have been developed to tackle this challenge. Among them, use transient directing group emerged as an effective tool, circumventing need extra synthetic steps install then cleave molecule. More recently, strategy successfully applied even more challenging transition-metal-catalyzed enantioselective functionalization. This review will highlight discuss main advances made chiral C(sp2)–H C(sp3)–H by transition-metal catalysis.

Language: Английский

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Transient directing ligands for selective metal-catalysed C–H activation

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(9), P. 646 - 659

Published: July 20, 2021

Language: Английский

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Pd^II–Catalyzed Site-selective β- and γ-C(sp³)–H Arylation of Primary Aldehydes Controlled by Transient Directing Groups

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 4727 - 4733

Published: March 14, 2022

Pd(II)-catalyzed site-selective β- and γ-C(sp3)-H arylation of primary aldehydes is developed by rational design L,X-type transient directing groups (TDG). External 2-pyridone ligands are identified to be crucial for the observed reactivity. By minimizing loading acid additives, ligand effect enhanced achieve high reactivities challenging aldehyde substrates. Site selectivity can switched from proximate relatively remote position changing bite angle TDG match desired palladacycle size. Experimental computational investigations support this rationale designing potentially C(sp3)-H functionalizations.

Language: Английский

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Rh(III)-Catalyzed Atroposelective C–H Selenylation of 1-Aryl Isoquinolines

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6009 - 6015

Published: April 5, 2024

Rhodium(III)-catalyzed atroposelective C–H selenylation of 1-aryl isoquinolines has been achieved. The direct reaction between and 2-(phenylselanyl)isoindoline-1,3-dione in the presence chiral SCpRh(III) complex afforded a series axially isoquinoline selenides up to 95% yield 96% ee. features mild conditions broad substrate scope. DFT calculations revealed that C–Se bond formation step proceeds through formal SN2 pathway.

Language: Английский

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A Chemistry for Incorporation of Selenium into DNA‐Encoded Libraries

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(32), P. 13273 - 13280

Published: April 13, 2020

Abstract Conventional direct C−H selenylation suffers from simple selenation with limited atom economy and complicated reaction system. In this work, we designed benzoselenazolone as a novel bifunctional selenide reagent for both off‐ on‐DNA under rhodium(III) catalysis. We show that using allowed production of series products containing an adjacent aminoacyl group in fast efficient way, high economy. The synthetic application method was demonstrated by taking advantage the amide functionality nucleophile, directing group, coupling partner. This work shows great potential facilitating rapid construction selenium‐containing DNA‐encoded chemical libraries (SeDELs), lays foundation development drugs.

Language: Английский

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Transient Directing Groups in Metal−Organic Cooperative Catalysis

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(56), P. 13899 - 13952

Published: July 19, 2021

The direct functionalization of C-H bonds is among the most fundamental chemical transformations in organic synthesis. However, when innate reactivity substrate cannot be utilized for a given single bond, this selective bond mostly relies on use directing groups that allow bringing catalyst close proximity to activated and these need installed before cleaved after transformation, which involves two additional undesired synthetic operations. These steps dramatically reduce overall impact attractiveness techniques since classical approaches based pre-functionalization are sometimes still more straightforward appealing. During past decade, different approach involving both situ installation removal group, can then often used catalytic manner, has emerged: transient group strategy. In addition its innovative character, strategy brought an unprecedented level usefulness enabled development remarkably efficient processes introduction functional onto aromatic aliphatic substrates. unlocked by will comprehensively overviewed review article.

Language: Английский

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Electrophotocatalysis Versus Indirect Electrolysis: Electrochemical Selenocyclization of 3‐Aza‐1,5‐dienes Facilitated by Energy Transfer, Direct Photolysis or N‐Hydroxyphthalimide

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(36)

Published: April 23, 2024

Three hybrid electrochemical protocols, which involve the energy transfer, direct photolysis and N-hydroxyphthalimide catalyst, respectively, are presented for selenylation/cyclization of fragile substrates 3-aza-1,5-dienes with diorganyl diselenides to afford 3-selenomethyl-4-pyrrolin-2-ones. The two electrophotocatalytic reactions indirect electrolysis one both regioselective external-oxidant- transition-metal-free, associated a broad substrate scope high Se-economy, all three methods amenable gram-scale syntheses, late-stage functionalizations, sunlight-induced experiments all-solar-driven syntheses.

Language: Английский

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Diorganyl diselenides: a powerful tool for the construction of selenium containing scaffolds

Dalton Transactions, Journal Year: 2021, Volume and Issue: 50(37), P. 12764 - 12790

Published: Jan. 1, 2021

Organoselenium compounds find versatile applications in organic synthesis, materials and ligand chemistry.

Language: Английский

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