Article
Chemistry, Applied
Julien C. Vantourout
Summary: This article discusses the applications of electrochemistry and transition metal catalysis in medicinal and process chemistry, explores the difficulties in scaling up transition metal electrocatalysis from the lab to the industry, and argues that intrinsic characteristics related to different electrocatalytic modes are responsible for the absence of transition metal electrocatalysis in large-scale process chemistry.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Multidisciplinary
Rui Wei, Shaoying Ju, Liu Leo Liu
Summary: We report a facile and highly modular access to an intriguing class of free Au-substituted phosphines (AuPhos). Au-substitution can boost the electron-releasing ability of AuPhos, leading to an electronically and sterically tunable, extremely electron-rich phosphorus center. Multi-nuclear transition metal complexes ligated by AuPhos are readily prepared, and preliminary catalytic results show the facilitation of C-N coupling reactions and decarbonylation reactions. This work provides insights for future development of electron-rich ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Khadijah Anwar, Kay Merkens, Francisco Jose Aguilar Troyano, Adrian Gomez-Suarez
Summary: Due to their abundance and ease of synthesis, alcohols are ideal for the selective derivatisation of organic molecules. Radical chemistry offers versatile strategies for the conversion of alcohols into various bonds, overcoming steric limitations associated with nucleophilic substitution pathways.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Siyuan Wang, Qilin Xue, Zhipeng Guan, Yayu Ye, Aiwen Lei
Summary: A manganese-catalyzed electrochemical intermolecular dehydrogenative cross-coupling reaction between aryl C-H and diphenyl phosphine oxides was reported in this study. By adjusting the proportion of substrates, a series of phosphorylation or diphosphorylation products could be obtained separately, without the need for external chemical oxidants. The research also indicated that C-H activation was not the rate-determining step.
Article
Chemistry, Organic
Min-Jie Zhou, Guixia Liu, Chen Xu, Zheng Huang
Summary: The dehydrogenation of saturated substrates is important for producing unsaturated organic molecules. Acceptorless C-C, C-N, and C-O bond desaturations have gained attention due to their high atom economy and environmentally benign nature. This review discusses the dehydrogenation of aliphatics, alcohols, and amines using two categories of homogeneous catalytic systems: thermal transition-metal-catalyzed two-electron pathway and photoredox catalyzed or electrochemically driven one-electron pathway.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Ruipu Zhang, Liubo Li, Kehan Zhou, Niankai Fu
Summary: Electrochemistry is a sustainable platform for studying radical-based reactions involving single-electron transfer. It offers a low-cost alternative to photochemistry by using electricity to drive electron flow. Paired electrolysis, which combines both anodic oxidation and cathodic reduction, is a promising approach to achieve redox-neutral reactions. However, the challenge lies in the gap between electrodes, making it difficult for reactive intermediates to react with their coupling partners. This concept article summarizes recent advances in overcoming this difficulty in radical-based convergent paired electrolysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Xiaolong Ma, Jinfeng Wei, Xu Yang, Huajin Xu, Yi Hu
Summary: Direct C-H bond functionalization is an effective technique for constructing C-X (X = C, N, O, S, etc.) and simplifying conventional synthesis methods. Transition-metal-catalyzed C-H bond functionalization requires metal catalysts, which hinders sustainable development. Recent studies have focused on transition-metal-free C(sp(3))-H bond functionalization. Electrochemistry, with its ability to replace traditional expensive and polluting metal salt oxidants with current/electrons, has gained attention. This review presents the systematic research on transition-metal-free electrochemical-induced C(sp(3))-H bond functionalization from 2016 to the present, highlighting future research hotspots and challenges in this field.
GREEN CHEMISTRY LETTERS AND REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Huaibo Zhao, Henry P. Caldora, Oliver Turner, James J. Douglas, Daniele Leonori
Summary: Aromatic aldehydes are important intermediates widely used in the chemical industry, but obtaining highly substituted derivatives can be challenging. This study presents a novel approach to assemble aromatic aldehydes from saturated precursors via a desaturative process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Arpana Tyagi, Naveen Yadav, Jabir Khan, Sanjay Singh, Chinmoy Kumar Hazra
Summary: Silicon-containing molecules have widespread applications in various research areas, and the transition-metal-free C-H silylation is an essential process for fabricating carbon-silicon bonds. This review focuses on recent developments in the field of silicon chemistry, particularly innovative transition-metal-free catalytic silylation using different strategies.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Tian Feng, Siyi Wang, Yin Liu, Shouzhuo Liu, Youai Qiu
Summary: This study presents a new method for the preparation of beta-substituted desaturated cyclic amines through electrochemical desaturative beta-functionalization, which is simple, robust, and exhibits good substrate tolerance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Energy & Fuels
Gourav Bhattacharya, Sam J. Fishlock, James A. McLaughlin, Susanta S. Roy
Summary: This concise review provides an overview of how metal-oxide-based wastes from industries like electronics and metal production are being utilized by the scientific community in energy storage, catalysis, and sensing applications. It focuses on E-waste, waste from metal production, and waste from metal recovery, discussing promising routes for obtaining high-quality metal-oxide nanoparticles and nanowires and addressing potential obstacles hindering widespread application.
INTERNATIONAL JOURNAL OF ENERGY RESEARCH
(2021)
Review
Chemistry, Multidisciplinary
Xu Cheng, Aiwen Lei, Tian-Sheng Mei, Hai-Chao Xu, Kun Xu, Chengchu Zeng
Summary: This review presents recent advances in electrochemical homogeneous catalysis, with a focus on electrochemical noble-transition-metal catalysis, photoelectrochemical catalysis, and electrochemical enantioselective catalysis. The topics discussed include the mechanism of noble metal catalysts in the presence of cathodic hydrogen evolution, the enhancement of redox properties in photocatalysis, and the regulation of enantioselectivity in catalytic electrochemical reactions.
Review
Chemistry, Organic
Jonas F. Goebel, Zhongyi Zeng, Lukas J. Goossen
Summary: The article summarizes recent advances in the synthesis of biaryls through electrooxidative processes, with a particular focus on electrooxidative C-H/C-M couplings and dehydrogenative couplings.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Dan Wang, Zhaohua Wan, Heng Zhang, Hesham Alhumade, Hong Yi, Aiwen Lei
Summary: A novel electrochemical reductive arylation method was developed for the efficient synthesis of various diarylamines without the need for transition-metal catalysts. The reaction could be scaled up efficiently in a flow cell, and several derivatization reactions were successfully carried out. Cyclic voltammetry experiments and mechanism studies revealed the roles of acetonitrile, formic acid, and triethyl phosphite in promoting this reductive arylation transformation.
Article
Chemistry, Multidisciplinary
Ming Chen, Guangbin Dong
Summary: This article describes a platinum-catalyzed desaturation of cyclic ketones to their conjugated alpha,beta-unsaturated counterparts, which operates under mild conditions without the need for strong bases or acids. The method shows good functional group tolerance and can be applied to diverse and complex structures. The mechanism involves fast and reversible alpha-deprotonation followed by a rate-determining beta-hydrogen elimination process, distinguishing it from prior palladium-catalyzed methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Longrui Chen, Lisa M. Barton, Julien C. Vantourout, Yinghua Xu, Chengpu Chu, Eric C. Johnson, Jesse J. Sabatini, Phil S. Baran
Summary: The study describes a scalable and safe route to synthesize a promising energetic material with a cyclobutane and four nitric ester groups. By utilizing streamlined preparation methods and safe reactions, the synthesis of the material was successfully achieved. Lessons learned from electrochemical scale-up provide important insights for future research.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Review
Chemistry, Organic
Ricardo Molina Betancourt, Pierre-Georges Echeverria, Tahar Ayad, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: This short review focuses on the development of efficient, atom-economical, and sustainable methods for the production of chiral alcohols and amines, particularly through homogeneous asymmetric catalysis. It discusses asymmetric hydrogenation and transfer hydrogenation, as well as dynamic kinetic resolution as key approaches to constructing up to three stereogenic centers.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Applied
Julien C. Vantourout
Summary: This article discusses the applications of electrochemistry and transition metal catalysis in medicinal and process chemistry, explores the difficulties in scaling up transition metal electrocatalysis from the lab to the industry, and argues that intrinsic characteristics related to different electrocatalytic modes are responsible for the absence of transition metal electrocatalysis in large-scale process chemistry.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Multidisciplinary
Yang Gao, David E. Hill, Wei Hao, Brendon J. McNicholas, Julien C. Vantourout, Ryan G. Hadt, Sarah E. Reisman, Donna G. Blackmond, Phil S. Baran
Summary: The electroreductive system has made the commonly used NHK coupling of vinyl-halides with aldehydes more practical, allowing for asymmetric reactions and involvement of non-canonical substrate classes. Detailed kinetics, cyclic voltammetry, and in situ UV-vis spectroelectrochemistry have revealed the subtle features of this mechanistically intricate process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Alfie G. Wills, Sylvain Charvet, Claudio Battilocchio, Christopher C. Scarborough, Katherine M. P. Wheelhouse, Darren L. Poole, Nessa Carson, Julien C. Vantourout
Summary: Electrochemical transformations involve complex interactions among various parameters, posing a challenge in developing robust and scale-independent reactions. High-throughput experimentation is a useful method for optimizing reactions and testing their robustness.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Multidisciplinary Sciences
Yazhong Huang, Kyle W. Knouse, Shenjie Qiu, Wei Hao, Natalia M. Padial, Julien C. Vantourout, Bin Zheng, Stephen E. Mercer, Javier Lopez-Ogalla, Rohan Narayan, Richard E. Olson, Donna G. Blackmond, Martin D. Eastgate, Michael A. Schmidt, Ivar M. McDonald, Phil S. Baran
Summary: This study presents a flexible and efficient platform for installing various phosphate linkages into oligonucleotides, utilizing readily accessible reagents and achieving diversity in linkage combinations. The platform easily accesses this diversity under a standardized coupling protocol with sustainably prepared, stable P(V) reagents.
Article
Chemistry, Organic
Tie-Gen Chen, Lucas Mele, Olivier Jentzer, Dominique Delbrayelle, Pierre-Georges Echeverria, Julien C. Vantourout, Phil S. Baran
Summary: A new approach using a radical retrosynthetic strategy to dissect the molecule into two halves is reported. By using reductive decarboxylative cross-coupling, a simple indoline can be coupled to a chiral pool-derived fragment to arrive at the target in only seven steps, avoiding the use of resolution strategies or asymmetric hydrogenation.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Kyle W. Knouse, Dillon T. Flood, Julien C. Vantourout, Michael A. Schmidt, Ivar M. Mcdonald, Martin D. Eastgate, Phil S. Baran
Summary: Phosphate linkages play a crucial role in various aspects of life, with high stability and enzymatically unlockable potential. Despite organic chemistry not fully embracing the potential of P(V) reagents, modern approaches in chemical oligonucleotide synthesis have already started to utilize them. The future holds numerous exciting opportunities for P(V) chemistry, offering new possibilities for the synthesis of molecules.
ACS CENTRAL SCIENCE
(2021)
Article
Chemistry, Applied
Sara Zahim, Kenny Delacroix, Agathe Carlier, Thierry Berranger, Julie Bergraser, Pierre-Georges Echeverria, Laurent Petit
Summary: This study describes the recent efforts to find an efficient and scalable route to tetrahydro-4H-pyran-4-one using commercially available starting materials. The work culminated in the preparation of over 20 kg of the title compound in the pilot plant facility.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Organic
Kevin Grollier, Clement Ghiazza, Anis Tlili, Thierry Billard, Maurice Medebielle, Julien C. Vantourout
Summary: A practical electrochemical method is reported in this study for the generation of CF3Se- anion from a stable reagent (TsSeCF3), enabling metal-free trifluoromethylselenolation of activated alkyl halides. Trifluoromethylselenolated compounds were obtained in moderate to excellent yields under optimized reaction conditions. Finally, cyclic voltammetric and F-19 NMR studies were conducted to gain insight into the reaction mechanism.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sylvain Charvet, Maurice Medebielle, Julien C. Vantourout
Summary: This article presents a systematic study of the manganese-mediated alpha-radical addition of carbonyl groups to olefins. Through optimization of conditions and development of a practical electrocatalytic reaction, the scope of the reaction was expanded and a predictive model was established.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Taline Kerackian, Didier Bouyssi, Guillaume Pilet, Maurice Medebielle, Nuno Monteiro, Julien C. Vantourout, Abderrahmane Amgoune
Summary: This article describes the development and in-depth study of a cross-electrophile coupling of alkyl N-acyl imides with alkyl halides using nickel catalysis and electrochemistry. The method utilizes the stability and easy access of N-acyl imides to selectively synthesize dissymmetric dialkyl ketones. Mechanistic studies reveal the generation of alkyl radicals through single-electron oxidation of alkyl bromides by electrogenerated (bpy)Ni(I) species. The reaction of alkyl N-acyl imides with (bpy)Ni(0) and (bpy)Ni(I) species leads to Ni(II) acyl intermediates. A comprehensive mechanistic picture of this selective cross-electrophile coupling is achieved through these investigations.
Article
Chemistry, Multidisciplinary
Yu Kawamata, Keun Ah Ryu, Gary N. Hermann, Alexander Sandahl, Julien C. Vantourout, Aleksandra K. Olow, La-Tonya A. Adams, Eva Rivera-Chao, Lee R. Roberts, Samer Gnaim, Molhm Nassir, Rob C. Oslund, Olugbeminiyi O. Fadeyi, Phil S. Baran
Summary: Target identification is crucial for early drug discovery but technically challenging. Photoaffinity labelling is commonly used but has limitations. Here, we introduce an electroaffinity labelling platform using a redox-active diazetidinone functional group for chemoproteomic-based target identification in live cells. This work demonstrates the effectiveness of the electrochemical platform for drug-target identification.
Article
Chemistry, Multidisciplinary
Yi Yang, Nathalie Saffon-Merceron, Julien C. Vantourout, Anis Tlili
Summary: We present a straightforward strategy for synthesizing unprecedented N-((trifluoromethyl)thio), N-(trifluoromethyl) amines using isothiocyanates, a fluoride source, and an electrophilic trifluoromethylthiolation reagent. The scalability of the methodology has been demonstrated, and the stability of the synthesized motif has been investigated.
