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

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Computational Methods Enable the Prediction of Improved Catalysts for Nickel-Catalyzed Cross-Electrophile Coupling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3043 - 3051

Опубликована: Янв. 26, 2024

Cross-electrophile coupling has emerged as an attractive and efficient method for the synthesis of C(sp2)–C(sp3) bonds. These reactions are most often catalyzed by nickel complexes nitrogenous ligands, especially 2,2′-bipyridines. Precise prediction, selection, design optimal ligands remains challenging, despite significant increases in reaction scope mechanistic understanding. Molecular parameterization statistical modeling provide a path to development improved bipyridine that will enhance selectivity existing broaden electrophiles can be coupled. Herein, we describe generation computational ligand library, correlation observed outcomes with features silico Ni-catalyzed cross-electrophile coupling. The new nitrogen-substituted display 5-fold increase product formation versus homodimerization when compared current state art. This yield was general several couplings, including challenging aryl chloride N-alkylpyridinium salt.

Язык: Английский

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A modular approach to stereoselective homoaldol reaction via photoredox/Cr/Co triple catalysis

Chem, Год журнала: 2024, Номер 10(3), С. 998 - 1014

Опубликована: Янв. 24, 2024

Язык: Английский

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Divergent Geminal Alkynylation–Allylation and Acylation–Allylation of Carbenes: Evolution and Roles of Two Transition-Metal Catalysts

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4727 - 4740

Опубликована: Фев. 8, 2024

Cooperative bimetallic catalysis to access novel reactivities is a powerful strategy for reaction development in transition-metal-catalyzed chemistry. Particularly, elucidation of the evolution two transition-metal catalysts and understanding their roles dual are among most fundamental goals catalysis. Herein, three-component terminal alkyne, diazo ester, an allylic carbonate was successfully developed via cooperative Cu/Rh with Xantphos as ligand, providing highly efficient 1,5-enynes all-carbon quaternary center that can be used immediate synthetic precursors complex cyclic molecules. Notably, Meyer–Schuster rearrangement involved reactions using propargylic alcohols, resulting unprecedented acylation–allylation carbenes. Mechanistic studies suggested course Cu(I) species might aggregate some types Cu clusters nanoparticles (NPs), while Rh(II)2 precursor dissociate mono-Rh species, wherein NPs proposed responsible alkynylation carbenes work cooperation Xantphos-coordinated dirhodium(II) or Rh(I)-catalyzed alkylation.

Язык: Английский

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Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11318 - 11331

Опубликована: Июль 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Язык: Английский

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Multiligand Enabled, Copper-Catalyzed Hiyama Coupling of Arylsilanes with Unactivated Secondary Alkyl Halides: Reaction Development and Mechanistic Insights

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A multiligand-involved Cu catalysis offers an efficient Hiyama coupling of arylsilanes with unactivated alkyl halides, where copper NHC and phenanthroline ligands were account for C(sp 2 )–Si activation )–C(sp 3 ) formation, respectively.

Язык: Английский

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Manganese/Cobalt Bimetallic Relay Catalysis for Divergent Dehydrogenative Difluoroalkylation of Alkenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Авг. 29, 2023

The involvement of manganese radical for halogen atom transfer (XAT) reactions has been esteemed as one reliable method but encountered with limited catalytic models. In this paper, a novel bimetallic relay catalysis Mn2 (CO)10 and cobaloxime developed divergent dehydrogenative difluoroalkylation alkenes using commercially available difluoroalkyl bromides. A wide range structurally diverse terminal, cyclic internal well tetrasubstituted are found to be good coupling partners deliver difluoroalkylated allylic products difluoromethylated products, accompanied the production H2 by-product. This strategy features broad substrate scope, mild reaction conditions excellent functional group compatibility. Its success represents an important step-forward expedite construction rich library products.

Язык: Английский

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Properties, Synthesis, and Characterization of Cu-Based Nanomaterials

ACS symposium series, Год журнала: 2024, Номер unknown, С. 1 - 33

Опубликована: Май 14, 2024

Copper-based nanomaterials offer a fascinating array of properties that make them pivotal in various technological applications. These materials, when scaled down to the nanoscale, exhibit enhanced electrical conductivity, surpassing their bulk counterparts. This book chapter primarily focuses on properties, synthesis, and characterization copper nanoparticles while also discussing metal oxide nanoparticles. Their large surface-to-volume ratios enable efficient electron transport, making valuable components electronics conductive inks for flexible devices. Furthermore, possess exceptional thermal crucial heat management advanced interface materials. Copper have positive economic environmental effects. catalytic render important diverse chemical reactions as energy storage systems like batteries supercapacitors. Additionally, tunability optical makes suitable photonic optoelectronic applications, ranging from sensors light-emitting The multifaceted copper-based continue drive innovation across broad spectrum industries.

Язык: Английский

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Implementation of micelle-enabled C(sp²)–C(sp³) cross-electrophile coupling in pharmaceutical synthesis

Chemical Communications, Год журнала: 2024, Номер 60(17), С. 2349 - 2352

Опубликована: Янв. 1, 2024

A sustainable C(sp 2 )–C(sp 3 ) cross-electrophile coupling was developed between readily available 5-bromophthalide and 1-benzyl-4-iodopiperidine under micellar conditions, leading to a key intermediate of one our development compounds.

Язык: Английский

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Enantioselective merged gold/organocatalysis

Chemical Communications, Год журнала: 2024, Номер 60(27), С. 3607 - 3623

Опубликована: Янв. 1, 2024

This highlight demonstrates the state of art in field enantioselective merged gold/organocatalysis by leveraging unique reactivity each catalyst.

Язык: Английский

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