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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Photoinduced Pd-Catalyzed Enantioselective Carboamination of Dienes via Aliphatic C–H Bond Elaboration

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 12053 - 12062

Published: April 16, 2024

Three-component diene carboaminations offer a potent means to access synthetically valuable allylic amines with rapid molecular complexity escalation. The existing literature primarily discloses racemic examples, necessitating the use of halides/pseudohalides as substrates. This paper introduces photoinduced Pd-catalyzed enantioselective three-component carboamination aryl-substituted 1,3-dienes, leveraging aliphatic C–H bonds for synthesis. reaction employs 10 mol % chiral palladium catalyst and an excess aryl bromide HAT reagent. approach yields diverse allylamines moderate excellent enantioselectivities. Notably, it stands first instance asymmetric reaction, directly utilizing abundant C(sp3)–H bearing partners, such toluene-type substrates, ethers, amines, esters, ketones. protocol exhibits versatility across encompassing aliphatic, aromatic, primary, secondary derivatives. method could serve versatile platform stereoselective incorporation various nucleophiles, dienes, partners.

Language: Английский

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O-Allylhydroxyamine: A Bifunctional Olefin for Construction of Axially and Centrally Chiral Amino Alcohols via Asymmetric Carboamidation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 8150 - 8162

Published: April 4, 2023

Difunctionalization of olefins offers an attractive approach to access complex chiral structures. Reported herein is the design N-protected O-allylhydroxyamines as bifunctional that undergo catalytic asymmetric 1,2-carboamidation with three classes (hetero)arenes afford amino alcohols via C-H activation. The C═C bond in O-allylhydroxyamine activated by intramolecular electrophilic amidating moiety well a migrating directing group. carboamidation reaction pattern depends on nature (hetero)arene reagent. Simple achiral reacted give centrally β-amino excellent enantioselectivity. employment axially prochiral or racemic heteroarenes afforded both axial and central chirality enantio- diastereoselectivity. In case heteroarenes, coupling follows kinetic resolution s-factor up >600. A nitrene-based mechanism has been suggested based experimental studies, unique mode induction diastereoselectivity proposed. Applications alcohol products have demonstrated.

Language: Английский

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Three-Component Fusion to Pyrazolo[5,1-a]isoquinolines via Rh-Catalyzed Multiple Order Transformation of Enaminones

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(7), P. 4833 - 4838

Published: March 22, 2023

A facile and practical method for the synthesis of fused tricyclic pyrazolo[5,1-a]isoquinolines has been realized via reactions enaminones, hydrazine hydrochloride, internal alkynes. By means Rh catalysis, extraordinary high-order bond functionalization, including transformation aryl C–H, ketone C═O, alkenyl C–N bonds in marks major feature cascade reactions. The results disclose individual advantage enaminones design novel efficient synthetic methods.

Language: Английский

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Cobalt(III)-Catalyzed Diastereo- and Enantioselective Three-Component C–H Functionalization

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(19), P. 11938 - 11944

Published: Sept. 13, 2021

Catalytic enantioselective C–H functionalization has recently become a tool for the creation of stereogenic centers. The steep increase in molecular complexity multicomponent reactions matches very well with asymmetric functionalizations, but realization such processes remains large challenge. We describe diastereoselective and highly three-component catalyzed by an earth-abundant Co(III) complex equipped chiral cyclopentadienyl ligand (Cpx). transformation provides rapid access to substituted β-hydroxyketones using three readily accessible starting materials. outlined reactivity CpxCo(III) catalysis shows higher exploitable propensity selective additions across carbonyls contrast chemistry Rh(III).

Language: Английский

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Rh(III)-Catalyzed Three-Component Syn-Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(14), P. 8585 - 8590

Published: June 30, 2021

Herein, we report a Rh(III)-catalyzed three-component carboamination of alkenes from readily available aryl boronic acids as carbon source and dioxazolones nitrogen electrophiles. This protocol provides facile access to valuable amine products including α-amino acid derivatives in good yield regioselectivity without the need for directing functionality. A series experiments suggest mechanism which Rh(III) catalyst undergoes transmetalation with acid, followed by turnover limiting alkene migratory insertion into Rh(III)-aryl bond. Subsequently, fast Rh-nitrene formation syn-carboamination product selectively after reductive elimination proto-demetalation. Importantly, coupling preference variety two-component undesired byproducts.

Language: Английский

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C–H bond activation and sequential addition to two different coupling partners: a versatile approach to molecular complexity

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6738 - 6756

Published: Jan. 1, 2022

Sequential multicomponent C–H bond addition is a powerful approach for the rapid, modular generation of molecular complexity in single reaction.

Language: Английский

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A Counterion/Ligand-Tuned Chemo- and Enantioselective Copper-Catalyzed Intermolecular Radical 1,2-Carboamination of Alkenes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(39), P. 18081 - 18089

Published: Sept. 26, 2022

The copper-catalyzed enantioselective intermolecular radical 1,2-carboamination of alkenes with readily accessible alkyl halides is an appealing strategy for producing chiral amine scaffolds. challenge arises from the easily occurring atom transfer addition between and issue enantiocontrol. We herein describe a alkene sulfoximines in highly chemo- manner. key to success this process conceptual design counterion/highly sterically demanded ligand coeffect promote exchange copper(I) forge C–N bonds radicals copper(II) complex. reaction covers bearing distinct electronic properties, such as aryl-, heteroaryl-, carbonyl-, aminocarbonyl-substituted ones, various precursors, including chlorides, bromides, iodides, CF3 source. Facile transformations deliver many building blocks interest organic synthesis related areas.

Language: Английский

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Intermolecular Redox-Neutral Carboamination of C–C Multiple Bonds Initiated by Transition-Metal-Catalyzed C–H Activation

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(23), P. 14754 - 14772

Published: Nov. 18, 2022

Carboamination of readily available feedstock-like alkenes, alkynes, and allenes has proven to be an efficient powerful tool for the synthesis diverse valuable amine derivatives relevance medicinal chemistry, biochemistry, material science. Among these developed carboamination methodologies, direct use C–H activation strategy leverage process is particularly attractive due ubiquity such bonds in organic molecules. In this review, we provide overview development intermolecular across C–C π-bonds initiated by a redox-neutral nonannulative manner, with emphasis on synthetic mechanistic aspects. principle, review summarized reactions key feature involving initial metalation followed migratory insertion into terminated electrophilic amination quenching, thus, it ordered sources C- N-based functionalities further divided π-compounds.

Language: Английский

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Three-Component Chemo-Selective Synthesis of N-(o-Alkenylaryl) Pyrazoles by Pyrazole Annulation and Rh-Catalyzed Chemo-Selective Aryl C–H Addition Cascade

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 8619 - 8627

Published: May 31, 2023

By using readily available enaminones, aryl hydrazine hydrochlorides, and alkynes as starting materials, the chemo-selective three-component synthesis of atropisomeric N-(o-alkenylaryl) pyrazoles has been efficiently accessed with rhodium catalysis. Unlike Satoh-Miura reaction leading to alkyne-based C-H benzannulation by prior prepared N-phenyl substrates, this protocol displays unprecedented selectivity alkenylation blocking second round metal key protonation step in presence acids.

Language: Английский

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