Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis

Organic Process Research & Development, Год журнала: 2023, Номер 27(7), С. 1160 - 1184

Опубликована: Март 20, 2023

Earth-abundant metal (EAM) catalysis can have profound impact in the pharmaceutical industry terms of sustainability and cost improvements from replacing precious metals like palladium as well harnessing differential reactivity first-row that allows for novel transformations to enable more efficient routes clinical candidates. The strategy building these capabilities within process group at Bristol Myers Squibb is described herein, with general plan a reaction screening platform, demonstrating scalability, increasing mechanistic understanding catalyst activation. development catalytic utilizing nickel, cobalt, iron while highlighting importance collaboration internal external groups advance EAM our portfolio. challenges benefits working transition metals, including metrics implementation catalysis, such cost, mass intensity, commercial availability catalysts ligands, are discussed.

Язык: Английский

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Selective C(aryl)–O bond cleavage in biorenewable phenolics

Chemical Society Reviews, Год журнала: 2024, Номер 53(11), С. 5489 - 5551

Опубликована: Янв. 1, 2024

Selective removal of the hydroxy, methoxy or both groups in biorenewable oxygenated arenes (derived from lignin depolymerization) provides, respectively, anisoles, phenols and benzenes.

Язык: Английский

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A decarbonylative approach to alkylnickel intermediates and C(sp ³ )-C(sp ³ ) bond formation

Science, Год журнала: 2024, Номер 385(6715), С. 1331 - 1337

Опубликована: Сен. 19, 2024

The myriad nickel-catalyzed cross-coupling reactions rely on the formation of an organonickel intermediate, but limitations in forming monoalkylnickel species have limited options for C(sp 3 ) cross-coupling. monoalkylnickel(II) from abundant carboxylic acid esters would be valuable, derivatives are primarily decarboxylated to form alkyl radicals that lack correct reactivity. In this work, we disclose a facile oxidative addition and decarbonylation sequence forms intermediates through nonradical process. key ligand, bis(4-methylpyrazole)pyridine, accelerates decarbonylation, stabilizes alkylnickel(II) destabilizes off-cycle nickel(0) carbonyl species. utility new reactivity )-C(sp bond is demonstrated reaction challenging by purely radical methods—the selective primary with iodides.

Язык: Английский

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Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 18, 2024

Abstract Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E ‐ or Z‐ from their complementary alkene feedstocks. However, the applicability of these methods has been hampered by lack generality, commercial availability precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for stereodivergent / Z ‐selective synthesis at room temperature. Commercial reagents enable this one‐carbon transposition ‐internal via Ni−H‐mediated insertion/elimination mechanism. Though mechanistic regime is same in both systems, underlying pathways that lead each active catalysts distinct, with catalyst forming comproportionation an oxidative addition complex followed substrate protonation metal trialkylphosphonium salt additive. In case, ligand sterics denticity control stereochemistry prevent over‐isomerization.

Язык: Английский

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Synthesis, Characterization, and Catalytic Activity of Ni(0) (DQ)dtbbpy, an Air-Stable, Bifunctional Red-Light-Sensitive Precatalyst

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

Опубликована: Фев. 5, 2025

Despite a well-established and growing body of work on nickel(0) precatalysts, the potential complexes as bifunctional precatalysts remains underexplored. In this study, we synthesized, characterized, evaluated catalytic activity (Ni(0)(DQ)dtbbpy), bifunctional, red-light-sensitive, air-stable complex. Owing to its unique photophysical properties, it effectively catalyzed etherification amination aryl bromides under 620–630 nm light irradiation, functioning both photocatalyst an active metal catalyst. Mechanistic studies density functional theory (DFT) calculations further confirmed exceptional absorption properties Ni(0)(DQ)dtbbpy in red-light region, well electron transfer process triggered by irradiation.

Язык: Английский

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Machine Learning-Guided Development of Trialkylphosphine Ni^(I) Dimers and Applications in Site-Selective Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15414 - 15424

Опубликована: Июль 6, 2023

Owing to the unknown correlation of a metal’s ligand and its resulting preferred speciation in terms oxidation state, geometry, nuclearity, rational design multinuclear catalysts remains challenging. With goal accelerate identification suitable ligands that form trialkylphosphine-derived dihalogen-bridged Ni(I) dimers, we herein employed an assumption-based machine learning approach. The workflow offers guidance space for desired without (or only minimal) prior experimental data points. We experimentally verified predictions synthesized numerous novel dimers as well explored their potential catalysis. demonstrate C–I selective arylations polyhalogenated arenes bearing competing C–Br C–Cl sites under 5 min at room temperature using 0.2 mol % newly developed dimer, [Ni(I)(μ-Br)PAd2(n-Bu)]2, which is so far unmet with alternative dinuclear or mononuclear Ni Pd catalysts.

Язык: Английский

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Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

Accounts of Chemical Research, Год журнала: 2024, Номер 57(3), С. 312 - 326

Опубликована: Янв. 18, 2024

ConspectusDue to the rarity of precious metals like palladium, nickel catalysis is becoming an increasingly important player in organic synthesis, especially for formation bonds with sp3-hybridized carbon centers. Traditionally, catalytic processes involving active Ni(0) species have relied on Ni(COD)2 or situ reduction Ni(II) salts. However, air- and temperature-sensitive material that requires use inert-atmosphere glovebox, protocols salts using metallic organometallic reductants add additional complications reaction development.This Account chronicles development air-stable precursors as replacements reduction. Based Schrauzer's seminal discovery Ni(COD)(DQ) zerovalent organonickel complex, our research laboratories at Scripps Research Bristol Myers Squibb developed a class precatalysts based Ni(COD)(EDD) (EDD = electron-deficient diene) framework, relying steric electronic properties supporting diene render metal center stable air, moisture, even silica gel but reactive ligand substitution redox changes.The complexes can be accessed through exchange Ni(COD)2, Ni(acac)2 DIBAL-H, electrochemically via cathodic followed by addition EDD one pot. As toolkit, demonstrate reactivity equivalent enhanced compared catalyzing C–C C–N cross-couplings, Miyaura borylations, C–H activations, other transformations. Since initial report Ni(COD)(DQ), its C(sp2)–CN activation, metallophotoredox, electric field-induced cross-coupling also been demonstrated.By incorporating precatalyst toolkit into campaigns, able perform C(sp3)–S(alkyl) couplings metallonitrenoid carboamination, both which represent challenging transformations were inaccessible traditional phosphine, nitrogen, olefin ligands. Computational experimental studies how quinone ligands are hemilabile, adopting η1(O)-bound geometries relieve strain stabilize transition states intermediates; redox-active, transiently oxidize center; electron-withdrawing -donating, depending oxidation state coordination geometry. These show enable key steps beyond imparting air-stability.Since documenting activity many observed unique this precatalyst. was found offer superior cross coupling form N,N-diaryl sulfonamides preparation biaryls from aryl halides benzene Ni-mediated, base-assisted homolytic aromatic substitution.

Язык: Английский

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Electrosynthesis of iminophosphoranes and applications in nickel catalysis

Chemical Science, Год журнала: 2024, Номер 15(16), С. 5980 - 5992

Опубликована: Янв. 1, 2024

N -Cyano iminophosphoranes are synthesized using electrochemistry and evaluated as ligands in various nickel-catalysed reactions. The electronic structural properties of these were studied both computationally experimentally.

Язык: Английский

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Base metal chemistry and catalysis

Cell Reports Physical Science, Год журнала: 2023, Номер 4(9), С. 101548 - 101548

Опубликована: Авг. 21, 2023

This perspective provides an entry-level conversation concerning base metal catalysis as a green and sustainable solution in industrial academic contexts. We establish definition of "base metal," challenging readers to consider the ethical implications sourcing. explore what it means be "sustainable" provide information on current efforts synthetic chemistry. examples catalytic trends transformations popular fields such cross-coupling small-molecule conversion, highlighting relevant systems. Finally, we social context—for example, decisions related catalyst development are often driven by factors including costliness, safety, adoptability (whether society will accept its usage), performance. How do move forefront? Is concerned if materials fabricated from cheaper more abundant sources? does chemistry community guide this knowledge translation?

Язык: Английский

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Advances in Accessing Rare Oxidation States of Nickel for Catalytic Innovation

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Nickel catalysis has experienced a renaissance over the past two decades, driven by its ability to access diverse oxidation states (0 +4). This review consolidates advancements in nickel chemistry at various states.

Язык: Английский

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