Review
Chemistry, Multidisciplinary
Juba Ghouilem, Morgane de Robichon, Franck Le Bideau, Angelique Ferry, Samir Messaoudi
Summary: Transition-metal-catalyzed C-H functionalization and photoredox nickel dual catalysis are innovative approaches for the synthesis of C-branched glycosides, providing efficient and mild methods for accessing a variety of complex C-branched glycosides of great interest.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Nelson Y. S. Lam, Kevin Wu, Jin-Quan Yu
Summary: The design of synthetic routes by retrosynthetic logic is influenced by available transformations. Transition-metal-catalyzed C-H activation is a powerful strategy for C-C bond formation, but its uptake in total synthesis has been tepid due to synthetic intractability and a lack of comprehensive guidelines. This Review addresses these issues and offers a guide to identify retrosynthetic opportunities to generate C-C bonds by C-H activation processes. Comparing traditional approaches and recent C-H activation methods, this Review demonstrates more efficient retrosynthetic strategies enabled by C-H activation for C-C bond construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Malcolm P. Huestis, Jean-Philippe Leclerc, Robin Larouche-Gauthier, Samuel Aubert-Nicol, Arun Yadav, Koilpitchai Sivamuthuraman
Summary: This study presents a rhodium(III)-catalyzed, site-selective, C-H alkylation of quinoline N-oxides at C8 using commercially available diazo Meldrum's acid, allowing for the synthesis of various 8-quinolinylacetic acid esters on gram scale without the need for excess air-sensitive organometallic reagents.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Pidiyara Karishma, Alisha Gogia, Sanjay K. Mandal, Rajeev Sakhuja
Summary: This study successfully achieved a direct carbocyclization of 2-aryl-2,3-dihydrophthalazine-1,4-diones using isocyanates as the carbonyl source via Ru(II)-catalyzed sequential ortho-amidation followed by intramolecular nucleophilic substitution, delivering substituted indazolo[1,2-b]phthalazine-triones in good-to-excellent yields. Additionally, excellent yields of the corresponding amidated products were obtained for ortho-substituted 2-aryl-2,3-dihydrophthalazine-1,4-diones by modifying the reaction parameters. The use of isocyanates as the carbonyl source, high functional group tolerance on the two coupling partners, and diverse chemical transformation of the synthesized fused and functionalized phthalazinones are the key highlights of this work.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Prabhat Kumar Baroliya, Mukesh Dhaker, Subir Panja, Shaeel Ahmed Al-Thabaiti, Soha M. Albukhari, Qana A. Alsulami, Arnab Dutta, Debabrata Maiti
Summary: Electrochemically promoted transition metal-catalyzed C-H functionalization is a promising area of research, but it is still at an early stage compared to traditional chemical-based oxidizing agents. Recent reports have shown increased attention on electrochemically promoted metal-catalyzed C-H functionalization. From the perspective of sustainability and cost effectiveness, electrochemically promoted oxidation of a metal catalyst offers a mild, efficient, and atom-economical alternative to traditional chemical oxidants. This Review discusses advances in the field of transition metal-electrocatalyzed C-H functionalization and how electricity enables metal-catalyzed C-H functionalization in an economic and sustainable way.
Article
Chemistry, Multidisciplinary
Jun-Jie Tian, Wei Sun, Rui-Rui Li, Gui-Xiu Tian, Xiao-Chen Wang
Summary: A borane/gold(I) co-catalytic system was designed and applied in C-H functionalization reactions and cycloaddition reactions between tertiary amines and alpha-alkynylenones, efficiently introducing a furan ring into the amine molecule.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Biochemistry & Molecular Biology
Pezhman Shiri, Atefeh Roosta, Wim Dehaen, Ali Mohammad Amani
Summary: The transition-metal-catalyzed C-H activation/annulation sequence has become a favorable tool for designing new synthetic strategies to produce indazoles, enabling the one-step synthesis of functionalized derivatives. The roles of some metal salts in the corresponding reaction mechanisms have not been identified.
Review
Chemistry, Multidisciplinary
Zijuan Yan, Pan-Lin Shao, Qing Qiang, Feipeng Liu, Xuchao Wang, Yongjie Li, Zi-Qiang Rong
Summary: This article summarizes various mechanisms and reaction conditions for the transition metal-catalyzed conversion of aldehydes to ketones.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Sara Lopez-Resano, Sara Martinez de Salinas, Felipe A. Garces-Pineda, Andrea Moneo-Corcuera, Jose Ramon Galan-Mascaros, Feliu Maseras, Monica H. Perez-Temprano
Summary: The potential access to Co-IV species to promote transformations challenging at Co-III in Cp*Co-catalyzed C-H functionalization reactions remains underexploited. We reveal the participation of Cp*Co-IV species in a Cp*Co-mediated C-S bond-reductive elimination through a combined experimental and computational strategy. These studies support the intermediacy of high-valent Cp*Co species in C-H functionalization reactions, particularly when involving nucleophilic coupling partners under oxidative conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Peng-Cheng Cui, Zheng-Chun Yin, Guan-Wu Wang
Summary: The visible-light-promoted C4-selective phosphorylation of unprefunctionalized pyridine and quinoline derivatives has been achieved. This Minisci-type protocol offers highly regioselective access to C4-phosphorylation products with good functional group tolerance and moderate to good yields via cross dehydrogenation coupling under mild conditions. Mechanistic studies demonstrate that the C4-phosphorylation products are obtained through a radical pathway.
Review
Chemistry, Physical
Prabhat Kumar Baroliya, Jaishri Chopra, Tanay Pal, Siddhartha Maiti, Shaeel Ahmed Al-Thabaiti, Mohamed Mokhtar, Debabrata Maiti
Summary: Supported metal nanoparticles have become an essential research area in catalysed chemical transformations, providing sustainable processes and efficient tuning of reactivity and recyclability. Various support materials have been investigated for their benefits in C-H functionalization, aiming to design efficient catalytic systems for future research.
Article
Chemistry, Organic
Jinkang Chen, Chuanliu Yin, Jian Zhou, Chuanming Yu
Summary: A new method for the synthesis of isoindolin-1-ones was developed through Co-catalyzed C-H/N-H functionalization and [4+1] annulation, showcasing its utility in late-stage modification of lithocholic acid derivatives and ibuprofen derivatives.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Shaheera Tabassum, Ameer Fawad Zahoor, Kulsoom Ghulam Ali, Muhammad Irfan, Syed Makhdoom Hussain, Rabia Akhtar
Summary: This review focuses on the transition metal-catalyzed C-H alkylation reactions, emphasizing the catalytic role of metals such as palladium, gold, scandium, silver, rhenium, and manganese. Various alkylating agents have been used to obtain the products in good yields.
JOURNAL OF THE IRANIAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Hui Yang, Ru Zhang, Su-Zhen Zhang, Qing Gu, Shu-Li You
Summary: Researchers have developed a series of chiral spiro ligands (BCSCp) from commercially available and cheap Bisphenol C, and prepared their corresponding rhodium complexes. These complexes have been successfully applied in enantioselective aryl C-H addition to nitroalkenes, producing C-H adducts with yields up to 88% and ee up to 98%.
Review
Chemistry, Multidisciplinary
Karunanidhi Murali, Luana A. Machado, Renato L. Carvalho, Leandro F. Pedrosa, Rishav Mukherjee, Eufranio N. Da Silva Junior, Debabrata Maiti
Summary: C-H functionalization has made significant advancements in synthetic organic chemistry, offering promising prospects in drug development and molecular architecture. The employment of novel metal catalysts and metal-free organic ligands has enabled selective activation of C-H bonds, overcoming previous challenges faced by chemists.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jonathan Trouve, Paolo Zardi, Shaymaa Al-Shehimy, Thierry Roisnel, Rafael Gramage-Doria
Summary: Utilizing secondary interactions between substrates and catalysts is a promising approach to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are often discovered through trial-and-error screening, as small stereo-electronic modifications within the substrate and catalyst can lead to vastly different reactivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Naba Abuhafez, Antoine Perennes, Rafael Gramage-Doria
Summary: This review article describes the recent advances in supramolecular catalysis involving metalloporphyrins as substrate recognition sites in the second coordination sphere of the catalyst. Inspired by host-guest phenomena, these catalytic systems exhibit unique activities, selectivities, and modes of action that are difficult to achieve using purely covalent strategies.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Matthieu Jouffroy, Thi-Mo Nguyen, Marie Cordier, Marielle Blot, Thierry Roisnel, Rafael Gramage-Doria
Summary: Direct reductive amination (DRA) is a widely used reaction in organic chemistry, aiming to convert carbonyl groups and amines into aminated compounds. The conventional method involves the use of a super stoichiometric amount of hazardous hydride reagents, which is incompatible with many sensitive functional groups. This study presents a new DRA method using iridium catalysis, overcoming the limitation of ketones with 2 degrees amines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Editorial Material
Chemistry, Multidisciplinary
Matthieu Jouffroy, Thi-Mo Nguyen, Marie Cordier, Marielle Blot, Thierry Roisnel, Rafael Gramage-Doria
Summary: This issue features an Ir-based catalytic system fueled by hydrogen for the direct reductive amination of ketones and secondary amines, allowing the preparation of complex aliphatic tertiary amines and expanding the chemical space.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Michele Tomasini, Lucia Caporaso, Jonathan Trouve, Jordi Poater, Rafael Gramage-Doria, Albert Poater
Summary: This study presents a non-biological catalyst that binds substrates via the induced fit model, with features reminiscent of enzymes. The research also reveals new elementary catalytic steps.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Purushothaman Rajeshwaran, Jonathan Trouve, Khalil Youssef, Rafael Gramage-Doria
Summary: The Wacker reaction is a significant industrial transformation that oxidizes olefins to ketones. However, it typically requires expensive palladium catalysts, which has led to the development of Wacker-type processes that avoid their use, allowing for more sustainable procedures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yang Sun, Kais Dhbaibi, Hortense Lauwick, Claudia Lalli, Gregory Taupier, Yann Molard, Rafael Gramage-Doria, Sylvie Derien, Jeanne Crassous, Mathieu Achard
Summary: A novel enantiopure pi-allylruthenium(IV) precatalyst was used for the enantioselective and stereospecific allylations of indoles, resulting in the synthesis of indolin-3-ones with vicinal stereogenic centers. The separation of diastereoisomers that exhibited opposite circularly polarized luminescence (CPL) activities in various solvents, including water, highlighted the potential of these sustainable transformations and the newly synthesized molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Erwan Prignot, Chanjuan Zhang, Olivier Jeannin, Zakaria Halime, Rafael Gramage-Doria, Franck Camerel
Summary: Metal-bis(dithiolene) complexes derived from Ni(II), Co(II), Pd(II), Pt(II) and Au(III) have been synthesized and characterized. Co(II) species are found to be dimeric in both solid state and solution, while Ni(II), Pd(II), Pt(II) and Au(III) coordination complexes exhibit monomeric structures. These metal-bis(dithiolene) complexes are highly stable in solution and retain their square planar geometry even when bound by pyridine derivatives.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jonathan Trouve, Rafael Gramage-Doria
Summary: In order to obtain new supramolecular ligands built around a zinc-porphyrin scaffold, we attempted to access sulfonyl triazole intermediates through copper-catalyzed click reactions. Unexpectedly, the presence of the zinc-porphyrin moiety prevents the formation of these triazole intermediates. Instead, the copper catalyst undergoes a different reaction pathway, reacting with trace amounts of alcohols or water in the media, leading to the formation of sulfonyl imidates or sulfonyl amides covalently connected to the zinc-porphyrin. Our study shows that copper-catalyzed click reactions can follow different mechanisms when occurring in close proximity to a zinc-porphyrin unit, which acts as a Lewis acid to stabilize otherwise inaccessible reaction intermediates.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Physical
Chanjuan Zhang, Erwan Prignot, Olivier Jeannin, Antoine Vacher, Diana Dragoe, Franck Camerel, Zakaria Halime, Rafael Gramage-Doria
Summary: In this study, nonionic dimeric cobalt-dithiolene complexes on a multiwall carbon nanotube/carbon paper electrode were shown to be efficient electrocatalysts for hydrogen production in aqueous media at pH 7. The high turnover numbers and increased cobalt concentration on the modified electrode suggest that immobilizing low-cost metal complexes on carbon material is a promising strategy for designing highly electroactive electrodes for green energy production.
Article
Chemistry, Organic
Yu-Chao Yuan, Qiu-Li Lu, Xiao-Tong Zhu, Sergio Posada-Perez, Miquel Sola, Albert Poater, Thierry Roisnel, Rafael Gramage-Doria
Summary: Selective C-H functionalization for the formation of C-N bonds is crucial in organic synthesis. A highly reactive ruthenium-based catalytic system utilizing biologically-relevant cyclic amides as weak directing groups is reported, showing excellent levels of selectivity. The use of dioxazolone derivatives as amidating reagents overcomes issues encountered with unstable azide derivatives and allows for reactions under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Jonathan Trouve, Khalil Youssef, Sitthichok Kasemthaveechok, Rafael Gramage-Doria
Summary: Iron catalysts enable Markovnikov-selective reactions, achieving up to 99% selectivity for ketone products from (hetero)aromatic and aliphatic olefins under ambient conditions. The catalyst design, inspired by the promiscuous activity of cytochromes P-450 enzymes, allows the formation of iron-hydride species under catalytically relevant conditions, leading to the desired selectivity.
Article
Chemistry, Organic
Kamil Kupietz, Jonathan Trouve, Thierry Roisnel, Samia Kahlal, Rafael Gramage-Doria
Summary: In this study, a novel bis-zinc-porphyrin compound with two macrocycles covalently connected by a short buta-1,3-diyne linkage was synthesized. The unexpected formation of this compound was explained by control experiments and an improved synthesis was achieved under copper-catalyzed Glaser-Hay coupling reaction conditions. This highly sterically congested bis-zinc-porphyrin derivative exhibited supramolecular host behavior and could encapsulate ditopic molecular guests with a high association constant.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ludivine Poyac, Stefano Scoditti, Xavier Dumail, Michel Granier, Sebastien Clement, Rafael Gramage-Doria, Charles H. Devillers, Sebastien Richeter
Summary: The electronic and steric properties of NHC ligands functionalized with porphyrins were investigated. It was found that when porphyrins are used as NHC-wingtips, the catalytic activity of the neighboring NHC-Rh(I) complex in the conjugate addition reaction is significantly improved.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Naba Abuhafez, Herve Ruffin, Raghu Kamaraj, Christian Bruneau, Rafael Gramage-Doria
Summary: A new method for the synthesis of 1,3-diene building blocks using ruthenium-catalyzed oxidative homo- and cross-coupling is reported, which mainly produces the E,E isomer. This methodology also allows for the synthesis of adipic acid ester derivatives in a one-pot fashion after in situ ruthenium-catalyzed hydrogenation.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)