A Bimolecular Homolytic Substitution-Enabled Platform for Multicomponent Cross-Coupling of Unactivated Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10274 - 10280

Published: April 3, 2024

The construction of C(sp3)–C(sp3) bonds remains one the most difficult challenges in cross-coupling chemistry. Here, we report a photoredox/nickel dual catalytic approach that enables simultaneous formation two linkages via trimolecular alkenes with alkyl halides and hypervalent iodine-based reagents. reaction harnesses bimolecular homolytic substitution (SH2) mechanism chemoselective halogen-atom transfer (XAT) to orchestrate regioselective addition electrophilic nucleophilic radicals across unactivated without need for directing auxiliary. Utility is highlighted through late-stage (fluoro)alkylation (trideutero)methylation C═C bearing different patterns, offering straightforward access drug-like molecules comprising sp3-hybridized carbon scaffolds.

Language: Английский

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Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 17, 2024

Abstract Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts metal reductant and the requirement installing directing group to suppress inherent β-H elimination bring great limitations this type reaction. We demonstrate herein that two different accessible via radical-anion relay Na 2 S O 4 as both sulfone-source. The together electron-shuttle catalyst crucial divert mechanistic pathway toward formation sulfone anion instead previously reported alkylmetal intermediates. Mechanistic studies allow identification carbon-centered radical sulfur-centered radical, which are in equilibrium capture or extrusion SO could be converted accelerated by iron catalysis, leading observed high chemoselectivity.

Language: Английский

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Ni- and Pd-Catalyzed Enantioselective 1,2-Dicarbofunctionalization of Alkenes

Synthesis, Journal Year: 2023, Volume and Issue: 56(01), P. 1 - 15

Published: June 12, 2023

Abstract Catalytic enantioselective 1,2-dicarbofunctionalization (1,2-DCF) of alkenes is a powerful transformation growing importance in organic synthesis for constructing chiral building blocks, bioactive molecules, and agrochemicals. Both two- three-component context, this family reactions generates densely functionalized, structurally complex products single step. Across several distinct mechanistic pathways at play these transformations with nickel or palladium catalysts, stereocontrol can be obtained through tailored ligands. In Review we discuss the various strategies, mechanisms, catalysts that have been applied to achieve enantioinduction alkene 1,2-DCF. 1 Introduction 2 Two-Component Enantioselective 1,2-DCF via Migratory Insertion 3 Radical Capture 4 Three-Component 5 6 Miscellaneous Mechanisms 7 Conclusion

Language: Английский

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Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4395 - 4406

Published: March 8, 2024

Asymmetric reductive three-component arylalkylation of alkenes via the radical relay method has been well established, while asymmetric migratory insertion strategy remains unexplored. We report enantioselective nickel-catalyzed cross-electrophile with aryl- and alkyl halides an integrated Heck carbometalation/radical cross-coupling sequence. This protocol employing a chiral Ni/PHOX catalytic system allows terminal internal to successfully engage exquisite control regio-, chemo-, stereoselectivity. More importantly, this undergoes regio- arylnickelation followed by Csp3–Csp3 elimination, thus exhibiting reverse regioselectivity method. Mild reaction conditions exceptional functional group tolerance facilitate method's compatibility bioactive motifs modular synthesis biologically active compounds. The experiments density theory calculations provide insights into mechanism origin stereoselectivity, hemilabile nature PHOX ligand is critical for achieving arylalkylation.

Language: Английский

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A dinuclear gold(I) complex with bis(N-heterocyclic carbene) ligands potentiated immune responses against liver cancer via ROS-driven endoplasmic reticulum stress and ferroptosis

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 110940 - 110940

Published: Feb. 1, 2025

Language: Английский

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Copper-Catalyzed Selective Amino-alkoxycarbonylation of Unactivated Alkenes with CO

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

Published: Feb. 17, 2025

1,2-Amino-difunctionalization reactions of alkenes allow the efficient introduction different functional groups and rapid construction valuable functionalized amines. In this respect, we report a copper-catalyzed 1,2-amino-alkoxycarbonylation unactivated with CO alkylamine precursors in presence Lewis acid additive. The novel protocol allows direct access to β-amino derivatives from easily available starting materials. presented methods feature high chemo- regioselectivities, good group tolerance, substrate scope including diverse bioactive compounds drug-like molecules. Mechanistic studies indicate that additive is key realizing umpolung addition nucleophilic aminyl radicals electron-rich alkenes, which represents an elegant activation strategy for radicals.

Language: Английский

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Enantioselective Ni‐Catalyzed Three‐Component Dicarbofunctionalization of Alkenes

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(18)

Published: Aug. 3, 2023

Abstract Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization alkenes has been well developed in recent years, which is used the area total synthesis natural products late‐stage modification drugs rapid incorporation sp 3 ‐enriched carbon centers. In this concept, significant breakthroughs field summarized, together with related mechanisms. Moreover, remaining challenges potential opportunities also highlighted.

Language: Английский

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Language: Английский

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P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13540 - 13560

Published: Oct. 6, 2023

Bidentate P,N ligands, integrating phosphine and nitrogen donors, are highlighted for their versatile characteristics, offering both electronic steric tunability. Their hemilabile nature, coupled with the ability to modulate properties through choice of donor atoms substituents, has expanded horizons chemical transformations. This Review focuses on Ni-catalyzed cross-coupling reactions mediated by ligands. The asymmetrical nature each atom playing a specific role in catalytic cycle, offers control, stability, unique regioselectivity processes. In particular, Ni/P,N-catalytic system exhibits remarkable reactivity π-substrates including alkenes, alkynes, allenes. A thorough mechanistic understanding these processes insights into trends future directions Ni/P,N-catalyzed reactions.

Language: Английский

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Iridium‐Catalyzed Remote Site‐Switchable Hydroarylation of Alkenes Controlled by Ligands

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 23, 2023

An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering the products functionalized at subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields with to excellent site-selectivities. The catalytic system showed functional group tolerance a broad substrate scope, including unactivated activated alkenes. More importantly, regioconvergent transformations mixtures isomeric were also successfully realized. results mechanistic studies demonstrate that reaction undergoes chain-walking process give [Ar-Ir-H] complex alkene. subsequent processes proceed through modified Chalk-Harrod-type mechanism via migratory insertion alkene into Ir-C bond followed C-H reductive elimination afford hydrofunctionalization site-selectively.

Language: Английский

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