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

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 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

Язык: Английский

---

Effect of 6,6′-Substituents on Bipyridine-Ligated Ni Catalysts for Cross-Electrophile Coupling

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6897 - 6914

Опубликована: Апрель 19, 2024

A family of 4,4′-tBu2-2,2′-bipyridine (tBubpy) ligands with substituents in either the 6-position, 4,4′-tBu2-6-Me-bpy (tBubpyMe), or 6 and 6′-positions, 4,4′-tBu2-6,6′-R2-bpy (tBubpyR2; R = Me, iPr, sBu, Ph, Mes), was synthesized. These were used to prepare Ni complexes 0, I, II oxidation states. We observed that 6′-positions tBubpy ligand impact properties complexes. For example, bulkier 6,6′-positions better stabilized (tBubpyR2)NiICl species resulted a cleaner reduction from (tBubpyR2)NiIICl2. However, hindered prevented coordination tBubpyR2 Ni0(cod)2. In addition, by using type (tBubpyMe)NiCl2 (tBubpyR2)NiCl2 as precatalysts for different XEC reactions, we demonstrated 6,6′-substituents lead major differences catalytic performance. Specifically, while (tBubpyMe)NiIICl2 is one most active catalysts reported date can facilitate reactions at room temperature, lower turnover frequencies containing ligands. detailed study on intermediates (tBubpy)Ni(Ar)I (tBubpyMe2)Ni(Ar)I revealed several factors likely contributed activity. whereas are low spin relatively stable, high-spin less stable. Furthermore, captures primary benzylic alkyl radicals more slowly than (tBubpy)Ni(Ar)I, consistent activity former catalysis. Our findings will assist design tailor-made Ni-catalyzed transformations.

Язык: Английский

---

Reductive alkyl-alkyl coupling from isolable nickel-alkyl complexes

Nature, Год журнала: 2024, Номер 634(8034), С. 585 - 591

Опубликована: Авг. 29, 2024

Язык: Английский

---

Kinetics and Mechanism of PPh₃/Ni-Catalyzed, Zn-Mediated, Aryl Chloride Homocoupling: Antagonistic Effects of ZnCl₂/Cl^–

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(43), С. 29913 - 29927

Опубликована: Окт. 18, 2024

The Ni/PPh

Язык: Английский

---

COBRA web application to benchmark linear regression models for catalyst optimization with few-entry datasets

Cell Reports Physical Science, Год журнала: 2024, Номер unknown, С. 102348 - 102348

Опубликована: Дек. 1, 2024

Язык: Английский

---

One-Pot Chlorination and Cross-Electrophile Coupling of Alcohols with Aryl Chlorides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Although alkyl alcohols and aryl chlorides are the two most abundant substrate pools for cross-electrophile coupling, methods to couple them remain limited. Herein we demonstrate a simple procedure in situ deoxychlorination of followed by XEC with chlorides. A broad scope can be achieved tuning rate reaction via halide exchange. Key success is identification 1-chloro-N,N,2-trimethyl-1-propenylamine as mild, noninterfering halogenation reagent.

Язык: Английский

---

Cross-Electrophile Coupling of Aryl Chlorides with Alkyl Chlorides Using Rotating Magnetic Field and Metal Rods

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

The pursuit of sustainable and environmentally benign methods techniques continues to challenge organic chemists. Herein, we report the development a novel approach in which electromagnetic induction could participate coupling chlorides using rotating magnetic field metal rods. In particular, describe application this strategy nickel-catalyzed cross-electrophile aryl with alkyl chlorides. Using these abundant commercially available organochlorides, such system allows reactions proceed broader scope than current protocols under mild conditions.

Язык: Английский

---

Evidence for a Unifying Ni^I/Ni^III Mechanism in Light-Mediated Cross-Coupling Catalysis

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 11, 2025

Advances in nickel catalysis have significantly broadened the synthetic chemists' toolbox, particularly through methodologies leveraging paramagnetic species via photoredox or electrochemistry. Key to these reactions is oxidation state modulation of single-electron transfer events. Recent mechanistic studies indicate that C(sp2)-heteroatom bond formations proceed NiI/NiIII cycles. Related C(sp2)-C(sp3) cross-couplings operate photocatalytic generation C-centered radicals and a catalytic cycle involves Ni0, NiI, NiIII species. Here, we show light-mediated nickel-catalyzed can be carried out without using exogenous catalysts but with photoactive ligand. In pursuit expanding scope couplings donor-acceptor ligands, identified complex capable catalyzing between aryl halides benzyltrifluoroborate salts. Mechanistic investigations provide evidence transmetalation photochemically generated NiI organoboron compound key step under conditions.

Язык: Английский

---

Translation of Nickel-Catalyzed C(sp²)–C(sp³) Cross-Electrophile Coupling to Non-Amide Solvents

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

The cross-electrophile coupling of organobromides is widely utilized in organic synthesis but generally requires undesirable amide solvents (e.g., DMF, DMA, and NMP). We report that the combination a strongly donating, bidentate nitrogen ligand, LiI, 4-picoline enables variety alcohol, ester, ethereal at up to 50 g scale. An improved optimal 4,4'-bis(dimethylamino)-2,2'-bipyridine, also reported on basis reductive homocoupling 4-dimethylamino-2-chloropyridine.

Язык: Английский

---

Virtual Ligand-Assisted Optimization: A Rational Strategy for Ligand Engineering

Опубликована: Апрель 25, 2024

Ligand engineering is one of the most important, but labor-intensive processes in development transition metal catalysis. Historically, this process has been streamlined by invention ligand descriptors such as Tolman’s electronic parameter and cone angle. Analyzing reaction outcomes terms these parameters enabled chemists to find important factors for designing optimal ligands. However, typical strategies analyses largely rely on regression approaches, which often requires many experimental data understand non-intuitive trends. Here, we introduce virtual ligand-assisted optimization (VLAO) method, a novel computational approach engineering. In features ligands are identified simple mathematical operations equilibrium structures and/or states interest, derivative values arbitrary objective functions with respect obtained. These then used guiding principle optimize within space. The VLAO method was demonstrated monodentate bidentate phosphine including asymmetric quinoxaline-based addition, successfully found highly selective α-selective hydrogermylation terminal ynamide according suggested design method. results would imply potential utility optimizing wide variety

Язык: Английский

---