Room temperature nickel‐catalyzed reductive coupling of end‐brominated polystyrene chains DOI

Jaden L. Chong,

Alisha M. Burch,

Danielle M. Otero

et al.

Journal of Polymer Science, Journal Year: 2023, Volume and Issue: 62(1), P. 146 - 154

Published: Oct. 28, 2023

Abstract Facile, room‐temperature coupling of brominated polymer chains can be accomplished in high yields (~80%) using a nickel‐based catalytic cycle that also includes magnesium and zinc. The extent ( X c ) was found to similarly when performed under vacuum or with nitrogen purge, although its effectiveness varied significantly as function the solvent, reagents, structure chain end. Kinetic studies show even at room temperature, nearly all occurs within first ~2 h reaction vacuum, accompanying color changes occurring system coinciding activity. One step mechanistic is proposed occur via chain‐end radical intermediates inserted into cycle, consistent addition trap essentially thwarting dimerization by capturing preventing inclusion reaction. presence aryl bromide functional groups, however, does not impede reaction, demonstrating catalyst's preference for alkyl bromides our conditions. impact necessity other components were explored, supporting importance MgCl 2 serving Lewis acid promote reactivity CBr end groups.

Language: Английский

Formation of C(sp2)–C(sp3) Bonds Instead of Amide C–N Bonds from Carboxylic Acid and Amine Substrate Pools by Decarbonylative Cross-Electrophile Coupling DOI
Jiang Wang, Lauren E. Ehehalt, Zhidao Huang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 9951 - 9958

Published: May 1, 2023

Carbon-heteroatom bonds, most often amide and ester are the standard method to link together two complex fragments because carboxylic acids, amines, alcohols ubiquitous reactions reliable. However, C-N C-O linkages a metabolic liability they prone hydrolysis. While C(sp

Language: Английский

Citations

38
Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp3–sp2 Carbon–Carbon Bonds DOI Creative Commons
James L. Douthwaite, Ruheng Zhao, Eunjae Shim

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10930 - 10937

Published: May 15, 2023

Amines and carboxylic acids are abundant synthetic building blocks that classically united to form an amide bond. To access new pockets of chemical space, we interested in the development amine-acid coupling reactions complement coupling. In particular, formation carbon-carbon bonds by formal deamination decarboxylation would be impactful addition synthesis toolbox. Here, report a cross-coupling alkyl amines aryl C(sp

Language: Английский

Citations

29
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis DOI Creative Commons
Lauren E. Ehehalt, Omar M. Beleh, Isabella C. Priest

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 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

Language: Английский

Citations

13
Mechanochemical Deoxyfluorination of Carboxylic Acids to Acyl Fluorides and Successive Mechanochemical Amide Bond Formation DOI

Zhengyu Zhao,

Sota Ikawa,

Soichiro Mori

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(9), P. 3565 - 3574

Published: Feb. 16, 2024

Diverse methods have been reported for the synthesis of acyl fluorides; however, an environmentally benign method fluorides remains underdeveloped. In this study, we developed solvent-free mechanochemical deoxyfluorination carboxylic acids to mediated by 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) using a ball mill. This facilitated high product yields in short reaction times even sterically challenged acids. We also realized coupling and amines as well TFEDMA-mediated direct with via sequential one-pot deoxyfluorination/coupling pathway. Furthermore, protocol was expanded include peptide synthesis. The efficiency protocol, terms speed, characteristics, favorable E-factor, aligns requirements current environmental policies.

Language: Английский

Citations

7
Ligand Relay for Nickel‐Catalyzed Decarbonylative Alkylation of Aroyl Chlorides DOI Creative Commons

Tian‐Zhang Wang,

Yu‐Qiu Guan,

Tianyu Zhang

et al.

Advanced Science, Journal Year: 2023, Volume and Issue: 11(9)

Published: Dec. 13, 2023

Abstract Transition metal‐catalyzed direct decarboxylative transformations of aromatic carboxylic acids usually require high temperatures, which limit the substrate's scope, especially for late‐stage applications. The development selective decarbonylative acid derivatives, most fundamental aroyl chlorides, with stable and cheap electrophiles under mild conditions is highly desirable meaningful, but remains challenging. Herein, a strategy nickel‐catalyzed alkylation chlorides via phosphine/nitrogen ligand relay reported. simple phosphine found essential decarbonylation step, while nitrogen promotes cross‐electrophile coupling. Such system can effectively orderly carry out catalytic process at room temperature, utilizing easily available as an aryl electrophile reductive alkylation. This discovery provides new coupling, features operationally simple, conditions, excellent functional group tolerance. approach applied to methylation various pharmaceuticals. Extensive experiments are carried provide insights into reaction pathway support process.

Language: Английский

Citations

13
Palladium-Catalyzed Decarbonylative Nucleophilic Halogenation of Acid Anhydrides DOI Open Access
Tian Tian,

Shuhei Uei,

Weidan Yan

et al.

Catalysts, Journal Year: 2025, Volume and Issue: 15(2), P. 191 - 191

Published: Feb. 19, 2025

In this study, we developed a palladium-catalyzed decarbonylative nucleophilic halogenation reaction using inexpensive and readily available acid anhydrides as substrates. This approach effectively circumvents the instability of acyl chlorides low reactivity fluorides. The Pd/Xantphos catalyst system exhibited excellent compatibility with thermodynamically kinetically challenging reductive elimination C–X bonds (X = I, Br, Cl) from Pd(II) intermediates. Notably, for electron-donating substrates, adopting an open significantly improved efficiency. positive effect may be due to reversible nature CO insertion deinsertion, which helps direct toward desired pathway by allowing generated exit system. Mechanistic studies suggest that proceeds through highly reactive halide intermediate, followed unimolecular fragment coupling (UFC) via decarbonylation or alternative involving formation activated anionic palladate complex in presence lithium halide.

Language: Английский

Citations

0
Decarbonylative C(sp2)–C(sp2) reductive cross-coupling of aroyl fluorides with aryl bromides by palladium/cobalt co-catalysis DOI
Chen He,

Zhiyong Song,

Wei Yao

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3012 - 3018

Published: Jan. 1, 2024

Herein, we report a decarbonylative C(sp 2 )–C(sp ) reductive cross-coupling of aroyl fluorides with aryl bromides by palladium and cobalt co-catalysis.

Language: Английский

Citations

3
Mechanism and Origin of Nickel-Catalyzed Decarbonylative Construction of C(sp2)–C(sp3) Bonds from Carboxylic Acids and Their Derivatives DOI
Dong Tian, Weipeng Zhao, Zheng‐Yang Xu

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Nickel-catalyzed arylation of carboxylic acids provides a ligand-controlled chemoselectivity-switchable method for the construction C(sp2)-C(sp3) bonds. Here, we employed density functional theory to provide detailed understanding mechanism and origin nickel-catalyzed carbonyl transformation. This reaction generates decarbonylation products through oxidative addition, activation C-C bonds, decarbonylation, binding alkyl radicals with Ni(III) complexes, final reduction elimination step. The bonds in aromatic carboxylate esters is more favorable than C-O bond because interaction between nickel catalyst π orbitals substrate's moiety during activation. induction effect ligand group together determines transfer tendency group.

Language: Английский

Citations

0
Catalytic Synthesis of Carbonyl Compounds Using Acyl Fluorides, Carbamoyl Fluorides, and Fluoroformates: An Overview DOI

Yujin Jung,

Yoonho Lee, Kwangmin Shin

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(5)

Published: Feb. 1, 2024

Abstract Acyl fluorides, carbamoyl fluorides and fluoroformates have been employed as efficient reagents in a number of organic syntheses. Their application catalytic transformations, however, began to be explored the early 2000s. Recently, these increasingly gained attention owing their unique reactivity diverse systems. This review aims overview advancements development processes, including transition‐metal catalysis, organocatalysis, cooperative NHC/photoredox where organofluorine compounds are acyl, carbamoyl, ester group donors.

Language: Английский

Citations

3
Magnesium-Mediated Cross-Electrophile Couplings of Aryl 2-Pyridyl Esters with Aryl Bromides for Ketone Synthesis through In Situ-Formed Arylmagnesium Intermediates DOI
Xiaowei Han, Yuan He,

Chao Gui

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13661 - 13668

Published: Sept. 9, 2024

Aryl 2-pyridyl esters could efficiently undergo cross-electrophile couplings with aryl bromides the aid of magnesium as a reducing metal in absence transition-metal catalyst, leading to unsymmetrical diaryl ketones modest good yields wide functionality compatibility. In addition, reaction be easily scaled up and applied late-stage modification biologically active molecules. Preliminary mechanistic study showed that coupling presumably proceeds through situ formation arylmagnesium reagents key intermediates.

Language: Английский

Citations

3