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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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

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Cobalt-Catalyzed Enantioselective C–H Arylation of Indoles

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(2), P. 798 - 806

Published: Jan. 10, 2022

Atropoisomeric (hetero)biaryls are scaffolds with increasing importance in the pharmaceutical and agrochemical industries. Although it is most obvious disconnection to construct such compounds, direct enantioselective C–H arylation through concomitant induction of chiral information remains extremely challenging uncommon. Herein, unprecedented earth-abundant 3d-metal-catalyzed atroposelective reported, furnishing rare atropoisomeric C2-arylated indoles. Kinetic studies DFT computation revealed an uncommon mechanism for this asymmetric transformation, oxidative addition being rate- enantio-determining step. Excellent stereoselectivities were reached (up 96% ee), while using unusual N-heterocyclic carbene ligand bearing essential remote substituent. Attractive dispersion interactions along positive C–H---π exerted by identified as key factors guarantee excellent enantioselection.

Language: Английский

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Palladium-Catalyzed Enantioselective β-C(sp³)–H Activation Reactions of Aliphatic Acids: A Retrosynthetic Surrogate for Enolate Alkylation and Conjugate Addition

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(4), P. 537 - 550

Published: Jan. 25, 2022

Enolate alkylation and conjugate addition into an α,β-unsaturated system have served as long-standing strategic disconnections for the installation of α- or β-substituents on carbonyl-containing compounds. At onset our efforts to develop C-H activation reactions organic synthesis, we set eye toward developing asymmetric β-C-H aliphatic acids with perspective that this bond-forming event could serve a more flexible retrosynthetic surrogate both canonical carbonyl-related transformations.In Account, describe early using strongly coordinating chiral oxazolines probe reaction mechanism stereochemical nature cleavage transition state. The characterization key reactive intermediates through X-ray crystallography computational studies suggested state Pd-OAc bonds being approximately coplanar optimum interaction. We then moved forward practical, weakly monodentate amide directing groups, necessary advance achieving native carboxylic acids. Throughout journey, gradual deconvolution between substrate's effect its intimate interplay ligand properties has culminated in design new classes ultimately allowed competency activation. These established importance acceleration Pd-catalyzed activation, where weak coordination is responsible positioning catalyst cleavage, while direct participation from bifunctional enthalpically stabilizing state.Building upon these principles, developed five ligands (MPAA, MPAQ, MPAO, MPAThio, MPAAM) enable enantioselective reactions, including carbon-carbon carbon-heteroatom bond formation. accumulated data indicate possessing point chirality are most effective imparting stereoinduction step, application which enabled desymmetrization subsequent functionalization enantiotopic carbon protons across range arylamides and, recently, free Progress design, conjunction enabling alkali metal countercations, led realization suite β-methyl now methylene C(sp

Language: Английский

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Palladium (II)‐Catalyzed C−H Activation with Bifunctional Ligands: From Curiosity to Industrialization

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: Feb. 29, 2024

Abstract In 2001, our curiosity to understand the stereochemistry of C−H metalation with Pd prompted first studies in Pd(II)‐catalyzed asymmetric activation (RSC Research appointment: 020 7451 2545, Grant: RG 36873, Dec. 2002). We identified four central challenges: 1. poor reactivity simple salts native substrates; 2. few strategies control site selectivity for remote bonds; 3. lack chiral catalysts achieve enantioselectivity via metalation, and 4. low practicality due limited coupling partner scope use specialized oxidants. These challenges necessitated new catalyst reaction development. For , we developed approaches enhance substrate–catalyst affinity together novel bifunctional ligands which participate accelerate cleavage step. site‐selectivity introduced concept systematically modulating distance geometry between a directing template, catalyst, substrate selectively access bonds. devised predictable stereomodels catalyst‐controlled enantioselective based on participation ligands. Finally, have varied catalytic manifolds Pd(II) accommodate diverse partners while employing practical oxidants such as peroxides. advances culminated numerous reactions, setting stage broad industrial applications.

Language: Английский

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Cobalt‐Catalyzed Enantioselective C−H Carbonylation towards Chiral Isoindolinones

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 11, 2024

Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed unprecedented catalyzed by inexpensive readily cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, parallel affording a broad range of chiral isoindolinones in good yields excellent enantioselectivities (up to 92 % yield 99 ee). synthetic potential this method was demonstrated asymmetric synthesis biological active compounds, such as (S)-PD172938 (S)-Pazinaclone. resulting also serve ligands cobalt-catalyzed annulation alkynes construct phosphorus stereocenter.

Language: Английский

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Remote site-selective arene C–H functionalization enabled by N-heterocyclic carbene organocatalysis

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(8), P. 900 - 911

Published: July 11, 2024

Language: Английский

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Aminative Suzuki–Miyaura coupling

Science, Journal Year: 2024, Volume and Issue: 383(6686), P. 1019 - 1024

Published: Feb. 29, 2024

The Suzuki-Miyaura and Buchwald-Hartwig coupling reactions are widely used to form carbon-carbon (C-C) carbon-nitrogen (C-N) bonds, respectively. We report the incorporation of a formal nitrene insertion process into reaction, altering products from C-C-linked biaryls C-N-C-linked diaryl amines thereby joining pathways same starting-material classes. A combination bulky ancillary phosphine ligand on palladium commercially available amination reagent enables efficient reactivity across aryl halides pseudohalides, boronic acids esters, many functional groups heterocycles. Mechanistic insights reveal flexibility order bond-forming events, suggesting potential for expansion aminative cross-coupling concept encompass diverse nucleophiles electrophiles as well four-component variants.

Language: Английский

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Rapid Construction of Tetralin, Chromane, and Indane Motifs via Cyclative C–H/C–H Coupling: Four-Step Total Synthesis of (±)-Russujaponol F

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(2), P. 687 - 692

Published: Jan. 4, 2021

The development of practical C–H/C–H coupling reactions remains a challenging yet appealing synthetic venture because it circumvents the need to prefunctionalize both partners for generation C–C bonds. Herein we report cyclative C(sp3)–H/C(sp2)–H reaction free aliphatic acids enabled by cyclopentane-based mono-N-protected β-amino acid ligand. This uses inexpensive sodium percarbonate (Na2CO3·1.5H2O2) as sole oxidant and generates water only byproduct. A range biologically important scaffolds, including tetralins, chromanes, indanes, can be easily prepared this protocol. Finally, application methodology is demonstrated concise total synthesis (±)-russujaponol F in four-step sequence starting from readily available phenylacetic pivalic through sequential functionalizations four C–H

Language: Английский

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Exploiting photoredox catalysis for carbohydrate modification through C–H and C–C bond activation

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(11), P. 782 - 805

Published: Sept. 21, 2022

Language: Английский

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