Recent Advances in Ni‐Catalyzed 1,1‐Difunctionalization of Unactivated Olefins

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(4), P. 593 - 602

Published: Dec. 7, 2023

Abstract Unactivated olefins rank amongst the most important feedstocks in organic synthesis. Their availability makes them particularly useful synthons for subsequent functionalization, a catalytic manner. Driven by popularity ascribed nickel catalysis as new tool to rapidly forge molecular architectures via one‐or two‐electron manifolds, recent years have witnessed significant advances Ni‐catalyzed olefin difunctionalization. While 1,2‐difunctionalization or remote functionalization “chain‐walk” become mature disciplines repurposing potential of building blocks, it was only recently that extensions this chemistry 1,1‐difunctionalization been possible. This review summarizes 1,1‐difunctionalization, holding considerable promise powerful strategy our ever‐growing synthetic repertoire.

Language: Английский

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The Progress of Reductive Coupling Reaction by Iron Catalysis

The Chemical Record, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 17, 2024

Abstract The transition metal catalyzed coupling reaction has revolutionized the strategies for forging carbon‐carbon bonds. In contrast to traditional cross‐coupling methods using pre‐prepared nucleophilic organometallic reagents, reductive reactions C−C bonds formation provide some advantages. Because both partners are reduced in final products a stoichiometric amount of reductant, this approach not only avoids need use sensitive species, but also provides an orthogonal and complementary access classical reaction. Notably, feature readily available fragments, promote good step economy, exhibit high functional group tolerance unique chemoselectivity, which have propelled their increasingly popular organic synthesis. recent years, due low price, minimal toxicity, environmentally benign character, iron‐catalyzed garnered significant attention from synthetic chemists pharmacologists, especially coupling. This review aims insightful overview advances reactions, illustrate possible mechanisms.

Language: Английский

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CuH-Catalyzed Reductive Coupling of Nitroarenes with Phosphine Oxides for the Direct Synthesis of Phosphamides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7848 - 7858

Published: May 29, 2024

A CuH-catalyzed reductive coupling of nitroarenes with phosphine oxides is developed, which produces a series phosphamides in moderate to excellent yields good functional group tolerance. Gram-scale synthesis and late-stage modification nitro-aromatic molecule niclosamide are also successfully conducted. The mechanism study shows that the nitro transformed after being reduced nitroso nucleophilic addition procedure involved during reaction.

Language: Английский

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Cathodic Deoxygenative Alkylation of Nitro(hetero)arenes with Organic Halides

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

Published: Jan. 28, 2025

We have realized a cathodic deoxygenative alkylation between nitro(hetero)arenes and organic halides, employing bis(pinacolato)diboron (B2pin2) LiCl as additives to trap stabilize the generated alkyl radicals carbanions, thereby facilitating efficient N-O cleavage selective C-N bond formation. The protocol offers an economical method for synthesis of multiple aromatic(hetero) amines, without need reactive reductants exclusion air moisture. Notably, is distinguished by scalability, broad functional group compatibility, safe mild conditions, demonstrating practicality in late-stage modification various bioactive compounds.

Language: Английский

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Copper-Catalyzed Reductive Hydroamination of Inactive Diarylacetylenes with Nitroarenes

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

Published: April 17, 2025

Reductive hydroamination of stable and readily available nitroarenes with unsaturated hydrocarbons represents practical access to amines. Herein, we report a simple Cu-catalyzed amine synthesis via the reductive inactive diarylacetylenes. A series diarylacetylenes are successfully transformed into secondary amines under mild conditions good functional group tolerance.

Language: Английский

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Photoinduced Site-Selective Aryl C-H Borylation with Electron-Donor-Acceptor Complex Derived from B2Pin2 and Isoquinoline

Molecules, Journal Year: 2024, Volume and Issue: 29(8), P. 1783 - 1783

Published: April 14, 2024

Due to boron’s metalloid properties, aromatic boron reagents are prevalent synthetic intermediates. The direct borylation of aryl C-H bonds for producing compounds offers an appealing, one-step solution. Despite significant advances in this field, achieving regioselective bond using simple and readily available starting materials still remains a challenge. In work, we attempted enhance the reactivity electron-donor-acceptor (EDA) complex by selecting different bases replace organic base (NEt3) used our previous research. To delight, when NH4HCO3 as base, have achieved mild visible-light-mediated reaction with exceptional regioselectivity (rr > 40:1 single isomers). Compared methodologies, protocol provides more efficient broader scope through use N-Bromosuccinimide. protocol’s good functional-group tolerance excellent enable functionalization variety biologically relevant novel cascade transformations. Mechanistic experiments theoretical calculations conducted study indicated that, certain arenes, might proceed new mechanism, which involves formation transient EDA complex.

Language: Английский

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Protocol for iron-catalyzed cross-electrophile coupling of aryl chlorides with unactivated alkyl chlorides

STAR Protocols, Journal Year: 2024, Volume and Issue: 5(1), P. 102846 - 102846

Published: Jan. 23, 2024

Organochlorides are a crucial class of electrophiles in organic synthesis. Here, we present protocol for the cross-electrophile coupling aryl chlorides with unactivated alkyl chlorides, facilitated by an iron/B

Language: Английский

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