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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Ni-Catalyzed Enantioselective Desymmetrization: Development of Divergent Acyl and Decarbonylative Cross-Coupling Reactions

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

Ni-catalyzed asymmetric reductive cross-coupling reactions provide rapid and modular access to enantioenriched building blocks from simple electrophile precursors. Reductive coupling that can diverge through a common organometallic intermediate two distinct families of products are particularly versatile but underdeveloped. Here, we describe the development bis(oxazoline) ligand enables desymmetrization meso-anhydrides. When secondary benzylic electrophiles employed, doubly stereoselective acyl proceeds give ketone with catalyst control over three newly formed stereogenic centers. Alternatively, use primary alkyl halides in presence an additional halogen atom transfer results decarbonylative alkylation β-alkyl acids. Analysis reaction rates for range both catalysts substrates supports notion tuning different activation steps is required enhanced performance. These studies illustrate how design Ni-acyl either or highlight dual systems be used engage unactivated coupling.

Language: Английский

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Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and power source, chemists are provided with system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds. Indeed, electroreduction offers alternative generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which untouchable traditional reduction methods. Meanwhile, reductive coupling extensively utilized both industrial academic settings due their ability swiftly, accurately, effectively construct C–C C–X bonds, present innovative approaches synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) requirement stoichiometric quantities agents, (b) scarce activation strategies inert substrates high potentials, (c) incomplete mechanistic elucidation, (d) challenges isolation intermediates. merging represents attractive approach address above limitations synthesis seen increasing use synthetic community over past few years.Since 2020, our group dedicated developing electroreductive cross-coupling using readily available small molecules, such arenes, CO2, D2O, value-added products. Electroreductive chemistry versatile powerful capacity precise selectivity control, allowed us develop three electrochemical modes lab: (1) An economically advantageous direct (EDR) strategy that emphasizes efficiency, achieves atom utilization, minimizes unnecessary atomic waste. (2) A class organo-mediated (EOMR) methods controlling reaction pathways. This allows modulation processes enhance efficiency selectivity. (3) metal-catalyzed (EMCR) method enables selective functionalization specific bonds functional groups under mild conditions, thereby occurrence side reactions. We commenced studies establishing organic-mediator-promoted carboxylation aryl alkyl halides. was then employed arylcarboxylation simple styrenes halides manner. electrolysis arenes epoxides CO2 carboxyl source achieved. Moreover, through adjustment we successfully accomplished deuteration olefins, unactivated enabling efficient formation D-labeled Finally, building on previous understanding developed series alkylation enable C(sp3)–C(sp3)

Language: Английский

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Ni-catalyzed cross-electrophile alkyl-alkyl coupling reactions

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Language: Английский

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Sulfonyl hydrazides as a general redox-neutral platform for radical cross-coupling

Science, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Language: Английский

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Synthesis of α‐N‐Heteroaryl Ketones by Nickel‐Catalyzed Chemo‐, Regio‐ and Enantioselective Carbonylation of Alkenes and N‐Alkenyl Heteroarenes

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Enantioenriched α-aminoketones serve as important substructures in life science and precursors for the synthesis of diverse value-added targets organic biochemistry. However, direct access to enantioenriched from simple readily available starting materials remains a formidable challenge. Herein, we report an unprecedented nickel-catalyzed asymmetric cross-coupling protocol α-N-heteroaryl ketones alkenes enamines presence carbon monoxide surrogate. The success this reaction relies on sorting two different along with control regio- enantioselectivity. This reductive-oxidative carbonylation unactivated featuring use surrogate allows gas-free streamlined assembly distinct alkenes.

Language: Английский

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Synthesis of α‐N‐Heteroaryl Ketones by Nickel‐Catalyzed Chemo‐, Regio‐ and Enantioselective Carbonylation of Alkenes and N‐Alkenyl Heteroarenes

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Abstract Enantioenriched α‐aminoketones serve as important substructures in life science and precursors for the synthesis of diverse value‐added targets organic biochemistry. However, direct access to enantioenriched from simple readily available starting materials remains a formidable challenge. Herein, we report an unprecedented nickel‐catalyzed asymmetric cross‐coupling protocol α‐ N ‐heteroaryl ketones alkenes enamines presence carbon monoxide surrogate. The success this reaction relies on sorting two different along with control regio‐ enantioselectivity. This reductive‐oxidative carbonylation unactivated featuring use surrogate allows gas‐free streamlined assembly distinct alkenes.

Language: Английский

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Configuration Retention in P-Trifluoromethyl Phosphine Enabled Rh(I)-Catalyzed Decarbonylative Coupling of Carboxylates and Boroxines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

As compared with asymmetric catalysis, the memory of chirality provides another promising strategy to introduce chiral centers in light numerous starting materials that can be accessed. Decarboxylative coupling has become an important for C-C or C-X bond formation over decades development its versatility and low cost structural diversity carboxylic acids. However, more general configuration retention this transformation seldom been studied. Here, we report a novel π acceptor-type ligand P-trifluoromethyl phosphine enabled Rh(I)-catalyzed decarbonylative carboxylates boroxines. The α-carbon fully retained chiral, cis-, trans-substrates. Several phosphine-Rh(I) carbonyl complexes were prepared their v(CO) values known complexes, which indicated π-accepting property is reaction.

Language: Английский

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Asymmetric Multi-Atom Insertion of Esters via Rh-Catalyzed Ring Opening of Oxabicyclic Alkenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Precise skeletal manipulation involving insertion, deletion, and replacement has garnered considerable attention within the synthetic chemistry community. Among these processes, multi-atom insertion reactions in acyclic compounds remain a formidable challenge, primarily due to low efficiency of fragment recapture after cleavage, which results from lack substrate-specific proximity during reconstruction stage. Here, we report an asymmetric reaction esters via Rh-catalyzed ring opening oxabicyclic alkenes, achieving excellent regio-, diastereo-, enantioselectivity. This approach enables efficient rapid construction molecular library with chiral hydroxy-dihydronaphthalene scaffold, showcasing atom-efficient reaction. Detailed density functional theory calculations reveal key mechanistic features stereoselectivity-determining model this transformation.

Language: Английский

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Nickel-Mediated Ring Expansion Reactions of Benzocyclobutenones for Selective Construction of 5,7-Dihydro-6H-dibenzo[a,c][7]annulen-6-ones and 1H-Isochromen-1-ones

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Herein, we report the development of a general ring expansion strategy that involves formal self-dimerization benzocyclobutenones (BCBs) through nickel catalysis. These self-dimerizations BCBs are efficient and scalable provide facile unique construction diverse seven-membered ketones 1H-isochromen-1-ones with high structural diversity. Moreover, solvent effects CO atmosphere play crucial role in promoting exclusion, which may address regioselectivity control toward (4 + 4 - 1) product, while NaOAc as an additive under N2 promoted 2) product formation.

Language: Английский

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