Asymmetric 2,3-Addition of Sulfinylamines with Arylboronic Acids Enabled by Nickel Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17587 - 17594

Published: June 24, 2024

Sulfinamides have been widely used in organic synthesis, with research on their preparation spanning more than a century. Despite advancements catalytic methodologies, creating sulfur stereocenters within these molecules remains significant challenge. In this study, we present an effective and versatile method for synthesizing diverse range of S-chirogenic sulfinamides through asymmetric aryl addition to sulfinylamines. By utilizing nickel complex as catalyst, process exhibits impressive enantioselectivity can incorporate various arylboronic acids at the position. The resulting synthetic are stable highly adaptable, allowing conversion variety sulfur-containing compounds. Our study also incorporates detailed experimental computational studies elucidate reaction mechanism factors influencing enantioselectivity.

Language: Английский

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Influence of the Counterion on the Activation of Nickel(σ-Aryl) Precatalysts

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

Published: Feb. 2, 2025

Language: Английский

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Ni-Catalyzed Cyanation of (Hetero)Aryl Electrophiles Using the Nontoxic Cyanating Reagent K₄[Fe(CN)₆]

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(8), P. 6459 - 6465

Published: April 5, 2025

A Ni-catalyzed cyanation of aryl halides using potassium ferrocyanide (K4[Fe(CN)6]) as a nontoxic cyanide source has been developed. Key features this method include the use biphasic aqueous conditions to overcome innate insolubility K4[Fe(CN)6] in organic solvents and bench-stable Ni(II) precatalyst combined with commercially available JosiPhos ligand that enhances practicality scalability reaction. The inclusion acidic additive tetrabutylammonium hydrogen sulfate was found improve reaction rate conversion. initial scope successfully demonstrated on range (hetero)aryl bromides, chlorides, sulfamates catalyst loadings low 2.5 mol %. This base-metal-catalyzed methodology further translated decagram synthesis pharmaceutical intermediate, usurping prior Pd-catalyzed process employed hazardous solvent pair (Zn(CN)2, DMAc).

Language: Английский

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Development of Robust, Efficient and Scalable Transition Metal Catalyzed Transformations: Translation of Reactions from Micromole to Multi-Kilogram Scale Processes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8317 - 8336

Published: May 2, 2025

Language: Английский

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Application of Primary Phosphine Oxides in Domino‐Phospha‐Aldol Reactions of Diketones

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(15), P. 3354 - 3360

Published: June 7, 2024

Abstract An approach for the preparation and stabilization of primary phosphine oxides is presented complementing previous methods in situ generation. Specifically, RP(O)H 2 where R=benzyl (Bn), cyclohexyl (Cy), 2‐naphthyl (2‐Naph), phenyl (Ph), tert ‐butyl ( t ‐Bu) was prepared by controlled oxidation corresponding presence ferrocene as stabilizing reagent. The were characterized using NMR MS studied twofold hydrophosphorylation diketones. domino‐phospha‐aldol reaction catalysed with 5 mol% sodium methoxide yielded five‐, six‐ seven‐membered heterocyclic tertiary a high degree stereoselectivity, confirmed single X‐ray diffraction.

Language: Английский

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Data-Driven Phosphine Ligand Design of Ni-Catalyzed Enantioselective Suzuki–Miyaura Cross-Coupling Reaction for the Synthesis of Biaryl Atropisomers: standing on the shoulder of Pd catalysis giants

Published: March 4, 2024

The Suzuki-Miyaura cross-coupling reaction is a cornerstone in organic synthesis, enabling the formation of carbon–carbon bonds with high efficiency and selectivity. This study represents groundbreaking advancement field by pioneering first enantioselective Ni-catalyzed Suzuki–Miyaura reactions for synthesis biaryl atropisomers. Employing data-driven approach, we have crafted novel N-protected Xiao-Phos ligand, which, conjunction commercially available Ni(COD)2, delivered unparalleled enantioselectivity reactivity under mild conditions. ligand design was meticulously guided an extensive examination existing literature on Pd-catalyzed asymmetric reactions, directing virtual screening subsequent experimental verification synthesized ligands single iteration. innovative N-Bn-Xiao-Phos exhibited impressive enantioselectivities coupled exceptional yields, showcasing versatility diverse array functional groups aryl boronic acids, accomplishing successful gram-scale synthesis. DFT computational studies provided profound insights into mechanism roots enantioselectivity, elucidating dynamic coordination modes chiral steric induction. breakthrough not only broadens horizons but also highlights immense potential machine learning judicious

Language: Английский

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Catalyst Deactivation Modes in Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions Using an NHC-Pyridonate Ligand

Published: June 5, 2024

The catalytic activity of an NHC-pyridonate-supported nickel(0) complex for Suzuki–Miyaura coupling aryl halides was evaluated. Product formation observed in the absence a basic additive. However, low turnover numbers resulted from competitive catalyst deactivation. nature deactivation—dimerization nickel(II) intermediate—was elucidated through combination NMR monitoring, direct synthesis, and X-ray diffraction. This discovery leveraged to identify additives that enable improved stability turnover, thereby highlighting both promise pitfalls associated with incorporating secondary-sphere modifications cooperative catalysis.

Language: Английский

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Recent developments in nickel catalyzed Suzuki-Miyaura C–C cross-coupling reaction

Inorganica Chimica Acta, Journal Year: 2024, Volume and Issue: 572, P. 122249 - 122249

Published: July 9, 2024

Language: Английский

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Advancing Base-Metal Catalysis: Developing Nickel Catalysis for the Direct Telescope of Miyaura Borylation and Suzuki–Miyaura Cross-Coupling Reactions

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(11), P. 4039 - 4045

Published: Oct. 19, 2024

The development of an efficient and general telescoped nickel-catalyzed Suzuki–Miyaura coupling (SMC) process from a borylation reaction to form Csp2–Csp2 bonds without isolation the intermediate aryl boronate has been long-standing interest for chemists. Most scalable borylation/SMC sequences currently use palladium catalysts in subsequent catalytic steps, yet ability utilize nickel potential greatly improve efficiency decrease cost while also improving sustainability. This work introduces SMC methodology that operates under homogeneous biphasic conditions minimize inhibition byproducts benefits addition methanol as cosolvent. These findings enabled one-pot, two-reaction method, which is demonstrated with variety complex heterocyclic partners both nucleophilic boronic acid electrophilic halide, including array bioactive molecules are representative pharmaceutical synthetic targets. A comparison this analogous palladium-catalyzed included guide future cases. decagram scale utilizing pharmaceutically relevant halides demonstrates its scalability.

Language: Английский

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Combining Hammett σ constants for Δ-machine learning and catalyst discovery

Digital Discovery, Journal Year: 2024, Volume and Issue: 3(12), P. 2487 - 2496

Published: Jan. 1, 2024

We present a simple and fast linear model for discovering organometallic catalysts the Suzuki–Miyaura cross-coupling reaction, using combinatorial approach.

Language: Английский

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