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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Metal-catalysed C–H bond activation and borylation

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(12), P. 5042 - 5100

Published: Jan. 1, 2022

Transition metal-catalysed direct borylation of hydrocarbons via C–H bond activation has received a remarkable level attention as popular reaction in the synthesis organoboron compounds owing to their synthetic versatility.

Language: Английский

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Recognition in the Domain of Molecular Chirality: From Noncovalent Interactions to Separation of Enantiomers

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(16), P. 13235 - 13400

Published: Aug. 2, 2022

It is not a coincidence that both chirality and noncovalent interactions are ubiquitous in nature synthetic molecular systems. Noncovalent interactivity between chiral molecules underlies enantioselective recognition as fundamental phenomenon regulating life human activities. Thus, represent the narrative thread of fascinating story which goes across several disciplines medical, chemical, physical, biological, other natural sciences. This review has been conceived with awareness modern attitude toward its consequences needs to be founded on multidisciplinary approaches disclose basis essential phenomena domain With primary aim discussing this topic an integrated way, comprehensive pool rational systematic information provided, concerns fundamentals chirality, description interactions, their implications processes occurring different contexts. A specific focus devoted enantioselection chromatography electromigration techniques because unique feature "multistep" processes. second motivation for writing make clear statement about state art, tools we have at our disposal, what still missing fully understand mechanisms underlying recognition.

Language: Английский

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Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 6810 - 6816

Published: April 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Language: Английский

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New horizons for catalysis disclosed by supramolecular chemistry

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7681 - 7724

Published: Jan. 1, 2021

Recent advancements in supramolecular catalysis are reviewed, which show the potential of related tools when applied to organic synthesis. Such recognized as innovative instruments that can pave way alternative synthetic strategies.

Language: Английский

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Transition Metal Catalysis Controlled by Hydrogen Bonding in the Second Coordination Sphere

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(14), P. 12308 - 12369

Published: May 20, 2022

Transition metal catalysis is of utmost importance for the development sustainable processes in academia and industry. The activity selectivity complexes are typically result interplay between ligand properties. As can be chemically altered, a large research focus has been on development. More recently, it recognized that further control over achieved by using “second coordination sphere”, which seen as region beyond direct sphere center. Hydrogen bonds appear to very useful interactions this context they have sufficient strength directionality exert second sphere, yet hydrogen dynamic, allowing fast turnover. In review we highlighted several key features bonding summarized use program sphere. Such bridging two ligands coordinated center effectively lead supramolecular bidentate ligands. addition, used preorganize substrate Both strategies catalysts with superior properties variety catalyzed transformations, including (asymmetric) hydrogenation, hydroformylation, C–H activation, oxidation, radical-type photochemical reactions.

Language: Английский

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Dispersion and Steric Effects on Enantio-/Diastereoselectivities in Synergistic Dual Transition-Metal Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(4), P. 1971 - 1985

Published: Jan. 20, 2022

Comprehensive computational studies were carried out to explore the mechanisms of enantioselective Cu/Pd and stereodivergent Cu/Ir dual-catalytic syntheses α,α-disubstituted α-amino acids (α-AAs). A chiral copper azomethine ylide undergoes facile α-allylation with racemic π-allylpalladium species or stereopure π-allyliridium complex stereoconvergently stereodivergently furnish single/double stereocenters, respectively. Stereoselectivity at α-center is controlled by facial selectivity respect prochiral nucleophile. Despite apparently similar transition-state assemblies, models distortion/interaction analyses disclose versatile modes stereoinduction wherein can face-selectively intercept metal−π-allyl intermediates utilizing attractive dispersion interactions and/or sterically caused distortions. Generation β-stereocenter in system relies on a stereospecifically generated allyliridium electronically branched-to-linear selectivity, while dual yields linear monochiral product due steric factors π–π stacking interactions. The demonstrate molecular level how ligand-encoded information transferred α-/β-sites resulting α-AAs mode regio-/stereoselection altered differences transition-metal-stabilized coupling partners. To facilitate stereoselective catalysis, suite analytical tools extract controlling for asymmetric induction demonstrated.

Language: Английский

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Transition metal–catalyzed remote C─H borylation: An emerging synthetic tool

Science Advances, Journal Year: 2023, Volume and Issue: 9(16)

Published: April 21, 2023

Transition metal–catalyzed C─H bond activation and borylation is a powerful synthetic method that offers versatile transformation from organoboron compounds to virtually all other functional groups. Compared the ortho-borylation, remote remains more challenging owing inaccessibility of these bonds. Enforcing metal catalyst toward bonds needs well-judged design through proper ligand development. This review article aims summarize recent discoveries for by employment new catalyst/ligand with help steric ligand, noncovalent interactions. It has been found now takes part in total synthesis natural products shorter route. Whereas, Ir-catalyzed predominant, cobalt also started affect this field sustainable cost-effective

Language: Английский

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Progress in design and applications of supramolecular assembly of 2,2′:6′,2″-terpyridine-based first row d-block elements

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 506, P. 215619 - 215619

Published: Feb. 16, 2024

Language: Английский

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Cobalt(III)-Catalyzed Enantioselective C–H Functionalization: Ligand Innovation and Reaction Development

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

ConspectusIn contrast to precious transition metals, such as palladium and rhodium, the development of novel chiral ligands for enantioselective C-H functionalizations catalyzed by earth-abundant, cost-effective, environmentally friendly 3d metals poses substantial challenges, primarily due variable oxidation states, intricate coordination patterns, limited mechanistic insights. In this Account, we summarize our research endeavors in three types Co(III) catalysis: pseudotetrahedral achiral Cp*Co(III)/chiral carbonyl acid (CCA) catalysis, situ-generated octahedral cobalt(III) via cobalt/salicyloxazoline (Salox) Co(II)/chiral phosphoric (CPA) cooperative achieved through strategic ligand design. Our initial objective was achieve functionalization Cp*Co(III) catalysts with external ligands, aiming circumvent laborious preparation CpxCo(III) complexes. To end, developed several CCA incorporating non-covalent interactions (NCIs) a crucial design element. Next, address limitations associated lengthy synthesis Cp-ligated complexes difficulties modification, explored concept situ generation catalysis using commercially available cobalt(II) salts tailor-made ligands. This exploration led two innovative catalytic systems, namely, Co(II)/Salox Co(II)/CCA sequential catalysis. The emerged versatile strategy, demonstrating excellent enantioselectivities across range asymmetric reactions construct various molecules central, axial, planar, inherent chirality. facile single step, along ease further enhances versatility applicability approach. Moreover, successfully applied cobalt/Salox electro- photochemical-catalyzed functionalization, electrons or oxygen traceless oxidant, thereby eliminating need stoichiometric chemical oxidants. Through studies reaction developments, elucidated detailed structure-enantioselectivity relationships which are expected inform future endeavors. Finally, Co(II)/CPA enabled spiro-γ-lactams olefination/asymmetric [4 + 1] spirocyclization. Mechanistically, establishment stereochemistry occurs during cyclization where CPA serves both neutral Brønsted acid, stereoinduction independent cleavage step. We anticipate that insights advancements Account will inspire innovations drive progress metal-catalyzed reactions.

Language: Английский

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