A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides DOI Creative Commons
Maite Molins Colomer, Javier Fernández-García, Xavier Berzosa

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер unknown

Опубликована: Дек. 8, 2024

Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past Ullmann-type reactions starting from aryl iodides. However, no procedures described activation of less reactive bromides. In this work, we successfully developed a method hydroxylation bromides promoted by copper reactor. Notably, presence both diamine ligand DMF is key reaction to proceed. An inorganic base such as Na2CO3 also improved yield minimizing formation side products. The setup has applied range disubstituted moderate good yields was tested under 24 h continuous operation, showing stable yields, thus proving robustness catalysis. Finally, lifetime reactor operating conditions calculated first time, that technology safe operate at industrial scale.

Язык: Английский

The E factor at 30: a passion for pollution prevention DOI Creative Commons
Roger A. Sheldon

Green Chemistry, Год журнала: 2023, Номер 25(5), С. 1704 - 1728

Опубликована: Янв. 1, 2023

Publication of the E Factor drew attention to problem waste in chemicals manufacture. Thirty yeas later it is abundantly clear that underlying cause global environmental problems, from climate change plastic pollution.

Язык: Английский

Процитировано

147
Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis DOI
Paul J. Chirik, Keary M. Engle, Eric M. Simmons

и другие.

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

Процитировано

41
Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis DOI Creative Commons
Sergio González‐Granda, Lorena Escot, Iván Lavandera

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Фев. 6, 2023

Abstract The combination of catalytic methods provides multiple advantages in organic synthesis, allowing access to diverse molecules a straightforward manner. Merging metal and enzyme catalysis is currently receiving great attention due the possibility assemble C−C coupling, olefin metathesis, hydration other reactions with exquisite stereospecificity displayed by enzymes. Thus, this minireview organized based on action species (Pd, Ru, Au, Ir, Fe…) different Special will be paid design sequential processes concurrent cascades, presenting solutions such as use surfactants or compartmentalization strategies for those cases where incompatibilities could hamper overall process.

Язык: Английский

Процитировано

38
Recent Advances in Nonprecious Metal Catalysis DOI
Michael C. Haibach, Shashank Shekhar, Tonia S. Ahmed

и другие.

Organic Process Research & Development, Год журнала: 2023, Номер 27(3), С. 423 - 447

Опубликована: Фев. 17, 2023

Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due lower cost, better sustainability, toxicity. With continual growth broad field nonprecious catalysis (NPMC), we have chosen highlight selected articles published from March June 2022 which intended examples NPMC that feel may be especially relevant development. We aim inspire academic industrial innovation through discussion herein.

Язык: Английский

Процитировано

23
Bayesian Optimization as a Sustainable Strategy for Early-Stage Process Development? A Case Study of Cu-Catalyzed C–N Coupling of Sterically Hindered Pyrazines DOI
Elena Braconi, Edouard Godineau

ACS Sustainable Chemistry & Engineering, Год журнала: 2023, Номер 11(28), С. 10545 - 10554

Опубликована: Июль 7, 2023

Bayesian optimization is a powerful machine learning technique that particularly well-suited for optimizing chemical reactions in the early stages of process development. It can efficiently explore vast reaction spaces and predict high-yielding conditions by evaluating only small number experiments. In this report, we investigated potential as tool to enhance sustainability synthesis. Specifically, focused on real-world early-stage development example: C–N coupling sterically encumbered bromo-pyrazines with amines. Our objective was identify sustainable utilize Earth-abundant copper catalysts non-hazardous solvents. We used optimizers various acquisition functions. assessed their performance identified key features affecting results. The optimized enabled synthesis range pyrazines pyridines moderate excellent yields.

Язык: Английский

Процитировано

23
Selective C(aryl)–O bond cleavage in biorenewable phenolics DOI
Gilles De Smet, Xing‐Feng Bai, Bert U. W. Maes

и другие.

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

Процитировано

12
Oxidative Substitution of Organocopper(II) by a Carbon-Centered Radical DOI

Yuecheng Weng,

Yuxuan Jin,

Jian Wu

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23555 - 23565

Опубликована: Авг. 8, 2024

Copper-catalyzed coupling reactions of alkyl halides are believed to prominently involve copper(II) species and radicals as pivotal intermediates, with their exact interaction mechanism being the subject considerable debate. In this study, a visible light-responsive fluoroalkylcopper(III) complex, [(terpy)Cu(CF3)2(CH2CO2tBu)] Trans-1, was designed explore mechanism. Upon exposure blue LED irradiation, Trans-1 undergoes copper–carbon bond homolysis, generating Cu(II) carbon-centered radicals, where radical then recombines intermediate, resulting in formation Cis-1, Cis isomer Trans-1. Beyond this, well-defined fluoroalkylcopper(II) intermediate ligated sterically hindered ligand isolated underwent full characterization electronic structure studies. The collective experimental, computational, spectroscopic findings work strongly suggest that organocopper(II) engages via an "oxidative substitution" mechanism, which is likely operational pathway for copper-catalyzed C–H trifluoromethylation reactions.

Язык: Английский

Процитировано

9
Escape from Palladium: Nickel-Catalyzed Catellani Annulation DOI

Jingfeng Huo,

Yue Fu,

Melody J. Tang

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 11005 - 11011

Опубликована: Май 15, 2023

While Catellani reactions have become increasingly important for arene functionalizations, they been solely catalyzed by palladium. Here we report the first nickel-catalyzed Catellani-type annulation of aryl triflates and chlorides to form various benzocyclobutene-fused norbornanes in high efficiency. Mechanistic studies reveal a surprising outer-sphere concerted metalation/deprotonation pathway during formation nickelacycle, as well essential roles base triflate anion. The reaction shows broad functional group tolerance enhanced regioselectivity compared corresponding palladium catalysis.

Язык: Английский

Процитировано

19
Copper-catalyzed asymmetric allylic substitution of racemic/meso substrates DOI Creative Commons
Jun Li, Junrong Huang, Yan Wang

и другие.

Chemical Science, Год журнала: 2024, Номер 15(22), С. 8280 - 8294

Опубликована: Янв. 1, 2024

The synthesis of enantiomerically pure compounds is a pivotal subject in the field chemistry, with enantioselective catalysis currently standing as primary approach for delivering specific enantiomers. Among these strategies, Cu-catalyzed asymmetric allylic substitution (AAS) significant and irreplaceable, especially when it comes to use non-stabilized nucleophiles (pK > 25). Although AAS prochiral substrates has also been widely developed, methodologies involving racemic/meso are highly desirable, undergo dynamic processes give single enantiomer products. Inspired by pioneering work Alexakis, Feringa Gennari groups, continuously employed deracemization desymmetrization enriched In this review, we mainly focus on developments over past two decades, providing an explicit outline ligands employed, scope nucleophiles, underlying their practical applications.

Язык: Английский

Процитировано

6
Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis DOI Creative Commons
Sergio González‐Granda, Lorena Escot, Iván Lavandera

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(18)

Опубликована: Фев. 6, 2023

Abstract The combination of catalytic methods provides multiple advantages in organic synthesis, allowing access to diverse molecules a straightforward manner. Merging metal and enzyme catalysis is currently receiving great attention due the possibility assemble C−C coupling, olefin metathesis, hydration other reactions with exquisite stereospecificity displayed by enzymes. Thus, this minireview organized based on action species (Pd, Ru, Au, Ir, Fe…) different Special will be paid design sequential processes concurrent cascades, presenting solutions such as use surfactants or compartmentalization strategies for those cases where incompatibilities could hamper overall process.

Язык: Английский

Процитировано

10