Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(12), P. 7692 - 7760

Published: May 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Language: Английский

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Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1224 - 1243

Published: Jan. 4, 2024

Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are paramount importance in quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions between two (hetero)arenes have emerged as a concise effective approach generating wide array bi(hetero)aryl fused heteroaryl structures. This innovative bypasses challenges associated with substrate pre-activation processes, thereby allowing creation frameworks were previously beyond reach using conventional Ar–X/Ar–M reactions. These inherent advantages ushered new design patterns molecules deviate from traditional methods. ground-breaking enables transcendence limitations repetitive material structures, ultimately leading to discovery novel high-performance In this Perspective, we provide an overview recent advances development materials through utilization We introduce several notable strategies domain, covering both directed non-directed strategies, dual chelation-assisted strategy ortho-C–H arylation/cyclization strategy. Additionally, shed light on role advancement Finally, discuss current existing protocols offer insights into future prospects field.

Language: Английский

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Strategic application of C–H oxidation in natural product total synthesis

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(11), P. 783 - 799

Published: Sept. 20, 2023

Language: Английский

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Mechanisms of C(sp3)–H and C=C selective oxidative heterofunctionalizations by non-heme Fe and Mn mimics of oxygenase enzymes

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 508, P. 215793 - 215793

Published: March 18, 2024

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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The crucial role of silver(i)-salts as additives in C–H activation reactions: overall analysis of their versatility and applicability

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(18), P. 6359 - 6378

Published: Jan. 1, 2023

This review discusses the important role of silver( i ) salts as additives in transition-metal catalyzed C–H activation, and depicts discussion about current shift towards Ag-free procedures, plausible sustainable alternatives.

Language: Английский

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Palladium-Catalyzed Annulations via Sequential C–H Activations of C(sp²)–H/C(sp³)–H or C(sp³)–H/C(sp³)–H Bonds

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6535 - 6546

Published: April 15, 2024

Palladium-catalyzed C–H annulation reactions represent a compelling strategy to construct complex ring systems with high step economy. While there are many approaches annulate structures by activation of single bond, transformations that proceed multiple bonds less explored. This is especially true for examples where one the reacting located at an sp3 center. However, exciting developments in palladium-catalyzed continue expand scope these and provide innovative strategies challenging carbon–carbon bonds. From discoveries, sequential activations have emerged as powerful tool access through C(sp2)–H/C(sp3)–H or C(sp3)–H/C(sp3)–H In this Perspective, we showcase recent use order highlight synthetic potential activation-enabled annulations inspire future disconnections diverse scaffold synthesis.

Language: Английский

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Transition‐Metal‐Catalyzed Selective Alkynylation of C−H Bonds

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(22), P. 4994 - 5027

Published: Sept. 23, 2021

Abstract Alkynylation reactions are one of the most sought‐after synthetic methodologies due to versatility C−C triple bond diversifications. Sonogashira coupling was widely used for synthesis alkynylated molecules; however, this methodology requires use previously halogenated substrates, which is a major drawback. To overcome issue, complimentary method, transition‐metal‐catalyzed C−H alkynylation, emerged as an alternative tool in recent years. Though initial reports required either specific directing groups or strong alkynylating agents effective functionalization, studies indicate that site selective alkynylations can be carried out using mild and readily available under moderate reaction conditions. In review, we explain transition metal cataluyzed alkynylation both C(sp 2 )−H 3 bonds by emphasizing mechanism. magnified image

Language: Английский

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Recent advances in the incorporation of CO₂ for C–H and C–C bond functionalization

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(23), P. 9283 - 9317

Published: Jan. 1, 2021

Functionalization with CO 2 : This tutorial review is focused on various approaches developed so far for functionalization of unsaturated C–C & C–H bonds using to achieve carboxylation, lactonization lactamization by metal and free methods.

Language: Английский

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S,O‐Ligand Promoted meta‐C−H Arylation of Anisole Derivatives via Palladium/Norbornene Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 31, 2022

Reversing the conventional site-selectivity of C-H activation processes provides new retrosynthetic disconnections to otherwise unreactive bonds. Here, we report a catalytic system based on palladium/norbornene and an S,O-ligand for meta-C-H arylation aryl ethers that significantly outperforms previously reported systems. We demonstrate unique ability this employ alkoxyarene substrates bearing electron donating withdrawing substituents. Additionally, ortho-substituted are well tolerated, overcoming "ortho constraint", which is necessity have meta-substituent achieve high reaction efficiency, by enlisting novel norbornene mediators. Remarkably, first time monoarylation alkoxyarenes achieved efficiently enabling subsequent introduction second, different coupling partner rapidly furnish unsymmetrical terphenyls. Further insight into mechanism was isolation characterization some Pd-complexes-before after meta activation-prior evaluation their respective activities.

Language: Английский

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