Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

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Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji–Trost Homologative Amination Reaction toward Allylic Amines

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18497 - 18505

Published: Aug. 9, 2023

A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds

Language: Английский

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Ni/Photoredox-Catalyzed Enantioselective Acylation of α-Bromobenzoates with Aldehydes: A Formal Approach to Aldehyde-Aldehyde Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 19909 - 19918

Published: June 12, 2024

The catalytic cross-coupling of identical or similar functional groups is a cornerstone strategy for carbon-carbon bond formation, as exemplified by renowned methods, such olefin cross-metathesis, Kolbe electrolysis, and various cross-electrophile couplings. However, methodologies coupling aldehydes─fundamental building blocks in organic synthesis─remain underdeveloped. While the benzoin-type condensation, first reported 1832, offers reliable route aldehyde dimerization, chemo- enantioselective nonidentical yet aldehydes remains an unsolved challenge. Herein, we report unified platform enabling highly aldehydes. By leveraging nickel photoredox catalysis tandem with discrete activation strategies each aldehyde, this mechanistically distinct approach facilitates union aldehyde-derived α-oxy radical acyl radical, photocatalytically generated from aldehyde. This novel enables modular access to enantioenriched α-oxygenated ketones two minimally differentiated aliphatic substituents, feat not achievable existing chemocatalytic biocatalytic techniques. synthetic utility method demonstrated its application streamlined asymmetric synthesis medicinally relevant molecules. Additionally, mechanistic investigations rationalize versatility exploit new pathways addressing long-standing challenges.

Language: Английский

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Radical acylation: concepts, synthetic applications and directions

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(4), P. 1056 - 1085

Published: Jan. 1, 2023

In this tutorial, reaction scopes, limitations and mechanisms of radical acylations are summarized discussed according to types catalytic systems.

Language: Английский

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Enantioselective nickel-catalyzed Mizoroki–Heck cyclizations of amide electrophiles

Chemical Science, Journal Year: 2024, Volume and Issue: 15(7), P. 2593 - 2600

Published: Jan. 1, 2024

The first asymmetric amide cross-couplings that rely on C–N bond activation using transition metal catalysis are reported. study establishes a new avenue in chemistry.

Language: Английский

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Nickel‐Catalyzed Enantioselective Decarboxylative Acylation: Rapid, Modular Access to α‐Amino Ketones**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Nov. 8, 2023

A new approach to the enantiocontrolled synthesis of α-amino ketone derivatives is disclosed by employing a decarboxylative acylation strategy. Thus, when an acyl chloride and α-amido-containing redox-active ester are exposed nickel catalyst, chiral ligand, metal reductant, α-amido ketones produced in good yield high ee. The reaction exhibits broad substrate scope, can be easily scaled up, applied dramatically simplify several known structures.

Language: Английский

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Ligand Relay for Nickel‐Catalyzed Decarbonylative Alkylation of Aroyl Chlorides

Advanced Science, Journal Year: 2023, Volume and Issue: 11(9)

Published: Dec. 13, 2023

Abstract Transition metal‐catalyzed direct decarboxylative transformations of aromatic carboxylic acids usually require high temperatures, which limit the substrate's scope, especially for late‐stage applications. The development selective decarbonylative acid derivatives, most fundamental aroyl chlorides, with stable and cheap electrophiles under mild conditions is highly desirable meaningful, but remains challenging. Herein, a strategy nickel‐catalyzed alkylation chlorides via phosphine/nitrogen ligand relay reported. simple phosphine found essential decarbonylation step, while nitrogen promotes cross‐electrophile coupling. Such system can effectively orderly carry out catalytic process at room temperature, utilizing easily available as an aryl electrophile reductive alkylation. This discovery provides new coupling, features operationally simple, conditions, excellent functional group tolerance. approach applied to methylation various pharmaceuticals. Extensive experiments are carried provide insights into reaction pathway support process.

Language: Английский

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Synthesis of Chiral α-Aryl Ketones by Photoredox/Nickel-Catalyzed Enantioconvergent Acyl Cross-Coupling with Organotrifluoroborate

Organic Letters, Journal Year: 2024, Volume and Issue: 26(4), P. 850 - 854

Published: Jan. 22, 2024

Photoredox/nickel-catalyzed enantioconvergent acyl cross-coupling of carboxylic derivatives with racemic secondary organotrifluoroborate was developed for the synthesis an enolizable chiral α-aryl ketone under mild neutral conditions. Moderate to high yields and good enantioselectivities were achieved.

Language: Английский

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Metallaphotoredox‐Catalyzed Enantioselective Cross‐Electrophile Coupling Using Alcohols as Reducing Agents

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 1, 2023

The cross-electrophile coupling (XEC) represents a powerful strategy for C-C bond formation. However, controlling the enantioselectivity in these processes remains challenge. Here, we report an unprecedented enantioselective XEC of α-amino acid derivatives with aryl bromides, enabled by alcohols as reducing agents via Ni/photoredox catalysis. This mechanistically distinct approach exploits ability photocatalytically generated α-hydroxyalkyl radicals to convert alkyl electrophiles corresponding that are then enantioselectively coupled bromides. readily scalable protocol allows modular access valuable enantioenriched benzylic amines from abundant and inexpensive precursors, is applicable late-stage diversification broad functional group tolerance. Mechanistic studies rationalize versatility this alcohol-based reactivity radical generation subsequent asymmetric cross-coupling. We expect cross-coupling will render general platform development appealing yet challenging XECs.

Language: Английский

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Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling To Access Chiral Secondary Benzylic Alcohols

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16134 - 16144

Published: Feb. 8, 2024

Transition-metal-catalyzed asymmetric cross-coupling represents a powerful strategy for C-C bond formation and the synthesis of enantiomerically pure molecules. Here, we report dual nickel/photoredox-catalyzed enantioselective reductive aryl halides with α-bromobenzoates, readily generated from aliphatic aldehydes, to provide diverse chiral secondary benzylic alcohols that are important motifs in bioactive natural products pharmaceuticals. This catalytic system features mild conditions, good functional group tolerance, broad substrate scope, excellent enantiocontrol, avoidance stoichiometric metal reductants, presenting great potential late-stage functionalization complex

Language: Английский

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