Aluminum-Containing Heterobimetallic Complexes as Versatile Platforms for Homogeneous Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12519 - 12542

Published: Sept. 11, 2023

Within the broader area of heterobimetallic catalysis, Al/M compounds (M = any metal) are promising for design and execution catalytic manifolds. This Perspective reviews recent advances in focusing on their applications. Topics include polymerization, epoxide activation carbonylation, C–H functionalization, other important transformations mediated by catalysts. In each case, mechanistic role aluminum site is highlighted. A broad range Al-containing metalloligands combinations included to construct this comprehensive perspective.

Language: Английский

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Controllable Skeletal and Peripheral Editing of Pyrroles with Vinylcarbenes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 10, 2024

Abstract The skeletal editing of azaarenes through insertion, deletion, or swapping single atoms has recently gained considerable momentum in chemical synthesis. Here, we describe a practical strategy using vinylcarbenes situ generated from trifluoromethyl vinyl N ‐triftosylhydrazones, leading to the first dearomative pyrroles carbon‐atom insertion. Furthermore, depending on used catalyst and substrate, three types peripheral reactions are also disclosed: α‐ γ‐selective C−H [3+2] cycloaddition. These controllable molecular provide powerful platform for accessing medicinally relevant CF 3 ‐containing ‐heterocyclic frameworks, such as 2,5‐dihydropyridines, piperidines, azabicyclo[3.3.0]octadienes, allylated readily available pyrroles. Mechanistic insights experiments density functional theory (DFT) calculations shed light origin substrate‐ catalyst‐controlled chemo‐ regioselectivity well reaction mechanism.

Language: Английский

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Transient Directing Groups in Metal−Organic Cooperative Catalysis

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(56), P. 13899 - 13952

Published: July 19, 2021

The direct functionalization of C-H bonds is among the most fundamental chemical transformations in organic synthesis. However, when innate reactivity substrate cannot be utilized for a given single bond, this selective bond mostly relies on use directing groups that allow bringing catalyst close proximity to activated and these need installed before cleaved after transformation, which involves two additional undesired synthetic operations. These steps dramatically reduce overall impact attractiveness techniques since classical approaches based pre-functionalization are sometimes still more straightforward appealing. During past decade, different approach involving both situ installation removal group, can then often used catalytic manner, has emerged: transient group strategy. In addition its innovative character, strategy brought an unprecedented level usefulness enabled development remarkably efficient processes introduction functional onto aromatic aliphatic substrates. unlocked by will comprehensively overviewed review article.

Language: Английский

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Nickel-catalyzed hydroarylation reaction: a useful tool in organic synthesis

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 5074 - 5103

Published: Jan. 1, 2022

The nickel-catalyzed hydroarylation reaction opens up new routes to access complex organic compounds in a highly regio and stereoselective fashion from easily available precursors, such as olefin, alkyne, arene, aryl halide, boronic acid.

Language: Английский

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Site-Selective C–H Arylation of 2-Pyridones via Pd/NBE Cooperative Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7762 - 7770

Published: May 3, 2024

The 4-aryl-2-pyridone scaffold is considered to be a privileged pharmacophore. Diversity-oriented synthesis of its derivatives pressing demand within the field medicinal chemistry. Herein, we report site-selective C–H arylation 2-pyridones via palladium/norbornene cooperative catalysis. success this research based on nucleophilicity and metalation properties exhibited by C5 position in 2-pyridones, an activated norbornene that was employed capture C5-palladation intermediate transfer it C4 position, resulting highly specific at position. This methodology showcases remarkable compatibility with readily available aryl bromides, enabling efficient diverse range functional scaffolds (46 examples) notable site selectivity, which will very useful drug discovery. Furthermore, approach successfully utilized for economically viable perlolidine analogues. Density theory calculations revealed preference bond activation 2-pyridones. In addition, insights into mechanism suggest oxidative addition reductive elimination bromides are crucial steps conversion.

Language: Английский

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Bimetallic anchoring catalysis for C-H and C-C activation

Science China Chemistry, Journal Year: 2021, Volume and Issue: 64(11), P. 1923 - 1937

Published: Sept. 17, 2021

Language: Английский

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Ni-catalyzed hydroarylation of alkynes with unactivated β-C(sp2)−H bonds

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 26, 2022

Hydroarylation of alkynes with unactivated C(sp2)-H bonds via chelated C-H metalation mainly occurs at γ-position to the coordinating atom directing groups stable 5-membered metallacycles, while β-C(sp2)-H bond-involved hydroarylation has been a formidable challenge. Herein, we used phosphine oxide-ligated Ni-Al bimetallic catalyst enable β-C-H hydroarylations rare 7-membered nickelacycle.

Language: Английский

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Ligand-ligated Ni–Al bimetallic catalysis for C–H and C–C bond activation

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(88), P. 12260 - 12273

Published: Jan. 1, 2022

Compared with non-ligated Ni-Al bimetallic catalysis, bifunctional ligand-ligated catalysis displays stronger synergism, not only affecting the electronic properties and steric hindrance of substrates, but also producing a directing effect for facile control reactivity, site selectivity enantioselectivity in activation C-H C-C bonds. This review will give brief summary research advances this field, highlighting development ligands their applications.

Language: Английский

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Bifunctional NHC-Promoted C2-Alkylation of Pyridine via Ni–Al Bimetallic-Catalyzed Hydroarylation of Unactivated Alkenes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(9), P. 6068 - 6075

Published: April 18, 2023

Achieving site-selective alkylation with pyridine under transition metal catalysis has remained a long-standing challenge, especially when using unactivated alkene as an alkylating reagent. We herein describe C2-alkylation of Ni–Al bimetallic and directing bifunctional N-heterocyclic carbene (NHC) ligand through hydroarylation alkenes. A broad range C2-alkylated pyridines various functionalities could be prepared in high efficiency (up to 99% yield) C2-selectivity, the scope heterocycles is not limited but can expanded other azines like pyrazines pyrimidines. Mechanistic studies suggest that NHC–Ni–Al–pyridine complex responsible for site selectivity control reductive elimination might rate-determining step.

Language: Английский

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Copper-Catalyzed Regioselective Imidation of 2-Pyridones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3048 - 3053

Published: April 5, 2024

We demonstrate a ligand- and glovebox-free regioselective direct C(3)–H imidation of 2-pyridones also benzylic-type bearing methyl substituent employing Cu(OAc)2·H2O as the catalyst N-fluorobenzenesulfonimide (NFSI) an imidating reagent. A broad range imidated 2-pyridone derivatives is made up to excellent yields. The present strategy operates well on gram scale, ensuing product can be readily subjected mono- bis-desulfonylation reactions.

Language: Английский

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