Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Language: Английский

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HFIP in Organic Synthesis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(15), P. 12544 - 12747

Published: July 17, 2022

1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability stabilize ionic species, transfer protons, and engage range of other intermolecular interactions. The use this exponentially increased the past decade become choice some areas, such as C–H functionalization chemistry. In review, following brief history HFIP an overview physical properties, literature examples reactions using or additive are presented, emphasizing effect each reaction.

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 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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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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Distal γ‐C(sp³)−H Olefination of Ketone Derivatives and Free Carboxylic Acids

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(31), P. 12853 - 12859

Published: May 9, 2020

Reported herein is the distal γ-C(sp3 )-H olefination of ketone derivatives and free carboxylic acids. Fine tuning a previously reported imino-acid directing group using ligand combination mono-N-protected amino acid (MPAA) an electron-deficient 2-pyridone were critical for substrates. In addition, MPAAs enabled acids to form diverse six-membered lactones. Besides alkyl acids, benzylic C(sp3 bonds also could be functionalized 3,4-dihydroisocoumarin structures in single step from 2-methyl benzoic derivatives. The utility these protocols was demonstrated large scale reactions diversification olefinated products.

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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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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Diastereoselective palladium-catalyzed functionalization of prochiral C(sp³)–H bonds of aliphatic and alicyclic compounds

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(16), P. 2612 - 2633

Published: Jan. 1, 2022

Advancements in the palladium-catalyzed functionalization of diastereotopic or prochiral C(sp 3 )–H bonds generating stereogenic centers and stereo-arrays aliphatic compounds have been highlighted.

Language: Английский

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Unified approaches in transition metal catalyzed C(sp³)–H functionalization: recent advances and mechanistic aspects

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Direct alteration of unactivated C–H bonds organic building blocks.

Language: Английский

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