Article
Chemistry, Multidisciplinary
Joachim Loup, Egor M. Larin, Mark Lautens
Summary: A reductive cyclization using ortho-vinylanilides for preparing N-heterocycles was catalyzed by an inexpensive and bench-stable iron complex at ambient temperature. The reaction likely involves hydromagnesiation of the vinyl group and trapping of the generated benzylic anion by an intramolecular electrophile. This method showed broad applicability in synthesizing substituted indoles, oxindoles, and tetrahydrobenzoazepinoindolone derivatives, with mechanistic studies revealing the reversibility of the hydride transfer step. The synthetic utility was further demonstrated by the formal synthesis of a bioactive compound and a group of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Hua-Dong He, Zhi-Kai Zhang, Hao-Bo Tang, Yuan-Qing Xu, Xiao-Bo Xu, Zhong-Yan Cao, Hao Xu, Yang Li
Summary: A practical method for the synthesis of N,N-dialkyl anilines via reductive dialkylation has been developed using inexpensive substrates and cheap NiI2 as the key promoter. This method demonstrates high functional group tolerance and can be used for the synthesis and modification of drugs or pesticides.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
David A. Cagan, Daniel Bim, Breno Silva, Nathanael P. Kazmierczak, Brendon J. McNicholas, Ryan G. Hadt
Summary: This study investigates the mechanism of Ni(II)-bpy aryl halide complexes and finds that structural control can regulate the potential energy surfaces of metal-to-ligand and ligand-to-metal charge transfer excited states, facilitating the process of excited-state bond homolysis. This provides a rational approach to utilize photonic energy in synthetic chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Kartic Manna, Tanusree Ganguly, Sujoy Baitalik, Ranjan Jana
Summary: This method enables a metal-free, visible-light- and triphenylphosphine-mediated intermolecular reductive amination between nitroarenes and boronic acids at ambient temperature without any photocatalyst. Mechanistically, a slow reduction of nitroarenes to a nitroso and, finally, a nitrene intermediate occurs that leads to the amination product with concomitant 1,2-aryl/alkyl migration from a boronate complex. A wide range of nitroarenes underwent C-N coupling with aryl/alkylboronic acids providing high yields.
Article
Chemistry, Organic
Fang Lv, Jing Xiao, Junchun Xiang, Fengzhe Guo, Zi-Long Tang, Li-Biao Han
Summary: For the first time, H3PO3 was utilized as both the reducing reagent and the promotor in reductive benzylation reactions with aryl aldehydes. The combination of H3PO3/I-2 enabled various aromatic aldehydes to undergo iodination reactions and Friedel-Crafts type reactions with arenes, easily producing benzyl iodides and diarylmethanes in good yields while also leading to intramolecular cyclization reactions to give corresponding cyclic compounds. This novel strategy offers advantages of easy-handling, low-cost, and metal-free conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zeyuan Wei, Hengxu Li, Yujie Wang, Qiang Liu
Summary: The reactivity of metal-hydride complexes can be controlled by modifying ancillary ligands. In this study, a versatile and efficient NHC-based NNC-pincer Mn catalyst was designed to enhance the hydride-donor ability and reduce steric hindrance. The newly developed catalyst showed higher activity than the corresponding NNP-pincer Mn catalyst, enabling successful hydrogenation of a wide range of polar unsaturated compounds under mild conditions. This work presents a rare example of a general phosphine-free Mn-catalyzed hydrogenation system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Chuhan Li, Shuo Song, Yuling Li, Chang Xu, Qiquan Luo, Yinlong Guo, Xiaoming Wang
Summary: A catalytic system utilizing a mixture of cobalt (II) iodide and potassium tert-butoxide has been discovered to be highly active for the hydroboration of vinylarenes and organic nitriles, producing diverse products with high yield and facilitating one-pot transformations. The activation strategy of alkoxide-pinacolborane combination effectively activates cobalt (II) iodide to generate catalytically active heterotopic cobalt catalysts in situ.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Carla Magallon, Oriol Planas, Steven Roldan-Gomez, Josep M. Luis, Anna Company, Xavi Ribas
Summary: This study investigates the intrinsic organometallic reactivity of iron within a tetradentate N3C macrocyclic ligand scaffold, leading to the stabilization of aryl-Fe species crucial in Fe-catalyzed cross-coupling and C-H functionalization processes. The synthesis of aryl-Fe-II complexes under light irradiation and moderate heating allowed for thorough spectroscopic characterization and investigation of their intrinsic reactivity.
Article
Chemistry, Organic
Zezhong Gao, Hang Wang, Chunlin Zhou, Ning Wang, Shangda Li, Gang Li
Summary: In this study, a new C-H functionalization method was reported for the remote site-selective C-H iodination via C(sp(2))-H/C(sp(2))-I metathesis. The mild iodinating reagent, 1-iodo-4-methoxy-2-nitrobenzene, was used to iodinate 2-aryl benzoic acid derivatives, including 2-(naphthalen-1-yl)benzoic acids and [1,1'-binaphthalene]-2-carboxylic acids, giving valuable iodinated products in a site- and chemo-selective manner.
Article
Chemistry, Organic
Rumpa Sarkar, Surya Kanta Samanta, Anila M. Menon, Deepak Chopra, Debabani Ganguly, Mrinal K. Bera
Summary: A mild and efficient method for synthesizing diverse substituted quinoline and quinolin-2-one derivatives was reported. In situ generated nickel boride proved to be an effective catalyst for the reductive cyclization reaction. The reaction exhibited broad substrate scope, mild conditions, consistent yield, and was tolerant to a wide range of functional groups. This intramolecular reductive cyclization protocol enables the preparation of a large number of quinoline and quinolin-2-one derivatives from milligram to multigram scale.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Pooja Jain, Nitesh Kumar, Vidya Avasare
Summary: A DFT study was conducted to investigate the mechanism of the Pd(0)-catalyzed functional group transposition between aroyl chlorides and aryl iodides. The results showed that the reaction proceeds through the formation of phosphonium salts and ligand-enabled C-P bond metathesis, followed by the transposition of functional groups via interpalladium ligand exchange.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jian-Xing Liang, Peng-Fei Yang, Wei Shu
Summary: In this study, a nickel-catalyzed Finkelstein reaction under mild conditions was reported, which can convert a wide range of aryl/alkenyl bromides as well as chlorides into corresponding iodides with broad functional group tolerance.
Article
Chemistry, Applied
Shashi Kant Verma, Anamika Prajapati, Manoj Kumar Saini, Ashok K. Basak
Summary: Readily accessible 2-aryloxybenzaldehydes and 2-(arylthio)benzaldehydes can undergo a sequence of reactions to form a wide variety of unsubstituted 9H-xanthenes and thioxanthenes in high yields when heated with a Lewis acid in diisopropyl ether. This reductive cyclization method is compatible with several important functional groups and allows for the selective reductive cyclization of the more electron-rich aryl ring of a 2,6-bis(aryloxy)benzaldehyde. The key feature of this transformation is the chemoselective reduction of a transient xanthylium ion in the presence of an aldehydic group via intermolecular hydride transfer from diisopropyl ether (solvent).
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Saideh Rajai-Daryasarei, Mir Sadra Hosseini, Saeed Balalaie
Summary: A novel and practical method for accessing saturated ketones from unsaturated ketone derivatives using a CS2/t-BuOK system in dimethyl sulfoxide (DMSO) is presented. The in situ generation of xanthate salt through the reaction of carbon disulfide and potassium tert-butoxide is crucial for this transformation. Deuterium-labeling experiments showed that DMSO can act as a hydrogen donor.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Guyue Liu, Feiyue Hao, Lingling Liang, Zhengneng Jin, Jiashou Wu
Summary: A practical and simple method for the hydrodehalogenation of halogenated carboxylic acid derivatives is developed using a DMSO/HCOONa·2H2O system. This method avoids the need for light irradiation, electrochemical apparatus, transition metals, radical initiators, strong bases, and additional additives. Control experiments suggest that HCOONa may act as a hydride donor through nucleophilic substitution or addition for the hydrodehalogenation process.
Article
Chemistry, Physical
Frederic Celerse, Theo Jaffrelot Inizan, Louis Lagardere, Olivier Adjoua, Pierre Monmarche, Yinglong Miao, Etienne Derat, Jean-Philip Piquemal
Summary: The study presents a novel multilevel enhanced sampling strategy based on GaMD, implementing GaMD multi-GPU acceleration and dual-water mode in Tinker-HP to speed up solvent-solute interactions. By coupling GaMD with Umbrella Sampling, the convergence time of PMF is reduced significantly, and the introduction of Adaptive Sampling further enhances convergence speed, making it applicable for large-scale biological system simulations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Editorial Material
Chemistry, Physical
Etienne Derat, Shina Caroline Lynn Kamerlin
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Biochemistry & Molecular Biology
Thomas Deis, Jeremy Forte, Louis Fensterbank, Gilles Lemiere
Summary: This study describes the synthesis of a chloromethylsilicate bearing two Martin's ligands and investigates its reactivity and rearrangement mechanism.
Article
Chemistry, Organic
Tobias E. Schirmer, Mehdi Abdellaoui, Aleksandr Savateev, Cyril Ollivier, Markus Antonietti, Louis Fensterbank, Burkhard Konig
Summary: Mesoporous graphitic carbon nitride (mpg-CN) is used as a photocatalyst for dual photoredox- and nickel-catalyzed cross-coupling reactions, enabling sustainable C(sp(2))-C(sp(3)) bond formation.
Article
Chemistry, Organic
Marc Petit, Cassandre C. Bories, Geoffrey Gontard, Marion Barbazanges, Etienne Derat
Summary: We achieved an efficient regio- and chemoselective dearomatization of N-heteroarenes using hydrido-cobalt catalysts. Mild conditions were employed and the reaction exclusively produced the silyl-1,2-dihydroheteroarenes in a wide range of N-heteroarenes. Quinolines and pyridines with electron-donating and electron-withdrawing substituents were compatible with this methodology. DFT calculations, NMR spectroscopic studies, and X-ray diffraction analysis demonstrated the importance of a second silane for the final step of the reaction.
Review
Chemistry, Multidisciplinary
Andres Felipe Leon Rojas, Sara Helen Kyne, Philip Wai Hong Chan
Summary: Late-transition-metal-based complexes are essential catalysts in chemical synthesis, as they can rapidly and efficiently increase molecular complexity from readily accessible substrates. The control over product selectivities achieved by these catalysts, in terms of chemoselectivity, diastereoselectivity, enantioselectivity, and site-selectivity, is remarkable and has enabled a wide range of functional group transformations.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Applied
Mehdi Abdellaoui, Thomas Deis, Maxim-Aleksa Wiethoff, Carlota Bahri, Gilles Lemiere, Cyril Ollivier, Louis Fensterbank
Summary: The introduction of methyl group and its labeled analogs on Csp(2)-centers is a challenging issue in synthetic chemistry. The difficulty to generate methyl radical and control its reactivity limits the development of reliable processes. In this study, we introduce Martin methylsilicates with hexafluorocumyl alcohol ligands as radical precursors for chemoselective methylation, enabling the access to various analogs in good yields.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Jiacheng Li, Lorenzo Carli, Sara Helen Kyne, Philip Wai Hong Chan
Summary: This study presents an efficient method for the synthesis of 1,2-diamines through the 4CzPN-catalysed a-aminoalkylation of azomethine imines by secondary and tertiary a-silylamines under blue light emitting diode (LED) light (456 nm). Achieved without the use of metals or additives at room temperature, the synthetic protocol provides product yields up to 99% and can be applied to the late-stage functionalisation of three drug molecules and the gram-scale preparation of one example.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Baptiste Neil, Lamine Saadi, Louis Fensterbank, Clement Chauvier
Summary: Benzylsilanes are widely used as stable synthetic intermediates in organic synthesis, but are mainly produced by stoichiometric procedures. Catalytic alternatives for silylation of benzylic C(sp(3))-H bonds are scarce due to the need for specialized directing groups and catalytic systems to compete with the kinetically-favored silylation of C(sp(2))-H bonds. In this study, we report the first general and catalytic-in-metal undirected silylation of benzylic C(sp(3))-H bonds under ambient, transition metal-free conditions using stable tert-butyl-substituted silyldiazenes (tBu-N=N-SiR3) as silicon source. The high activity and selectivity of the catalytic system is attributed to the facile generation of organopotassium reagents, including tert-butylpotassium.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Alexandre Millanvois, Choon-Hong Tan, Cyril Ollivier, Louis Fensterbank
Summary: In this study, the synthesis of a Martin silicate with a pentafluoroethyl chain is reported for the first time, and the full characterization of this new pentacoordinated silicon species is provided. Insights into its electronic properties are given based on structural, physicochemical, and computational data. A comparative study of its reactivity in solution and in solid state by mechanochemistry is performed to evaluate its potential as a safe C2F5-alkylation reagent in nucleophilic or radical reactions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Marion Barbazanges, Yves Gimbert, Louis Fensterbank
Summary: This study reveals the importance of gold catalyst and reaction parameters in the addition of propargyl acetates to olefins via an O-acyl migration/ cyclopropanation sequence. The stereochemical outcome of the olefin can be selectively controlled by carefully choosing the reaction conditions, resulting in the formation of E- and Z-isomers.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Maxim-Aleksa Wiethoff, Mehdi Abdellaoui, Thomas Deis, Vincent Corce, Gilles Lemiere, Cyril Ollivier, Louis Fensterbank
Summary: The article presents a cross-coupling methodology using nickel-catalyzed connection between an aryl moiety and an alkyl radical generated from a silicate formed from a Martin spirosilane by photoinduced single-electron oxidation. In contrast to other anionic radical precursors, Martin silicates enable the direct engagement of highly reactive alkyl radicals in smooth C(sp(2))- C(sp(3)) bond-formation reactions.
Article
Chemistry, Multidisciplinary
Victor Dupont, Stephanie Ognier, Gabriel Morand, Cyril Ollivier, Louis Fensterbank, Michael Tatoulian
Summary: Amine derivatives, including aniline and allylic amines, can be synthesized in a single-step process using benzene and ammonia plasma in a microreactor. The influence of different process parameters such as temperature, residence time, and plasma power on the reaction yield and selectivity towards aminated products is evaluated. Simulation studies are conducted to propose a global mechanism and understand the role of various process parameters. The direct amination of benzene is demonstrated with a yield of 3.8% and selectivity of 49% under optimized conditions, and the influence of double bonds, conjugation, and aromatization on the amination mechanism is studied.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Education & Educational Research
Sara H. Kyne, Martin M. H. Lee, Charisse T. Reyes
Summary: Recent developments in digital technologies, including learning analytics, are changing educational practices by utilizing the wealth of information available to inform academic interventions. In this study, personalized feedback emails were sent to students in large undergraduate chemistry courses, using learning analytics to inform the content. The findings suggest that students who received personalized emails were more likely to pass their first-year chemistry course, fostering higher student success within the cohort.
CHEMISTRY EDUCATION RESEARCH AND PRACTICE
(2023)
Article
Chemistry, Multidisciplinary
James Theodore Merrett, Xiaoyu Chen, Sara Helen Kyne, Mandeep Harode, Philip Wai Hong Chan
Summary: This study describes a synthetic method for preparing 2,3-dihydro-1H-benzo[f]indoles using a rhodium(i)-catalysed cycloisomerisation/6π electrocyclisation of 5-(ethylnylamino)pent-2-yn-1-yl esters. The reaction mechanism involves the formation of a rare in situ rhodacycle in rhodium catalysis, which is susceptible to a formal 1,8-acyloxy migration-initiated reductive elimination. The proposed 1,4-allenene then undergoes a 6π electrocyclisation to give the N-heterocyclic product.
NEW JOURNAL OF CHEMISTRY
(2022)
