Article
Chemistry, Multidisciplinary
Joshua M. Paolillo, Alana D. Duke, Emma S. Gogarnoiu, Dan E. Wise, Marvin Parasram
Summary: A photoexcited-nitroarene-mediated anaerobic C-H hydroxylation of aliphatic systems was reported. The success of this reaction was attributed to the dual functionality of the photoexcited nitroarene as both the C-H bond activator and the oxygen atom source. Compared to previous methods, this approach is cost-effective and atom-economical due to the commercial availability of the nitroarene. The anaerobic conditions of the transformation allow for a significant expansion in substrate scope compared to prior reports. Mechanistic studies revealed the involvement of successive hydrogen atom transfer and radical recombination events, leading to N-arylhydroxylamine ether intermediates and key oxygen atom transfer products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yizhen Liu, Weishi Dong, Zhen Hua Li, Huadong Wang
Summary: The selective functionalization of methane under relatively mild conditions is achieved in this study, with the activation of methane leading to the conversion of methane to MEBcat through a synthetic cycle. The study demonstrates the potential of using non-metal elements for sustainable and less environmentally impactful transformations.
Article
Chemistry, Physical
Xiaoguang Zhou, Santanu Malakar, Thomas Dugan, Kun Wang, Aaron Sattler, David O. Marler, Thomas J. Emge, Karsten Krogh-Jespersen, Alan S. Goldman
Summary: A highly efficient catalyst for acceptorless dehydrogenation of alkanes was reported, featuring an iridium acetate complex with a fluorinated Phebox ligand. Computational studies shed light on possible mechanistic pathways, improving our understanding of this catalyst's behavior. The role of Na+ as a cocatalyst in promoting dechelation and lowering energy barriers was highlighted, along with the electrophilic nature of the reaction and the stability of the fluorinated catalyst.
Article
Chemistry, Multidisciplinary
Shuwen Zhao, Xiaojia Cai, Yuying Lu, Jinhui Hu, Zhuang Xiong, Jingwei Jin, Yin Li, Honggen Wang, Jia-Qiang Wu
Summary: A mild, selective, and redox-neutral C-H activation/annulation reaction of salicylaldehydes with fluorovinyl tosylates is reported. The use of monofluorovinyl tosylate leads to the synthesis of C2- and C3-substitution-free chromones, while difluorovinyl tosylate results in the construction of C2-fluoroalkoxy chromones. The reaction exhibits mild conditions and good functional-group tolerance.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Min Wu, Haiman Zhang, Ting Wang, Shuang Lin, Ziyang Guo, Hui Gao, Zhi Zhou, Wei Yi
Summary: In this study, the Rh(III)-catalyzed chemo-, regio-, and stereoselective carboamination of sulfonyl allenes has been achieved. This reaction utilizes N-phenoxy amides or N-enoxy imides as both C and N sources, and proceeds via a redox-neutral tandem C-H activation/allene insertion/oxidative addition/C-N bond formation pathway, enabling the direct construction of allylamine derivatives with an alpha-quaternary carbon center. The protocol demonstrates high atom-economy and good substrate compatibility, highlighting its synthetic potential for late-stage C-H modification of complex molecules.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Tyler P. Pabst, Paul J. Chirik
Summary: Cobalt precatalysts for the meta-selective borylation of fluorinated arenes were developed, achieving high turnover and selectivity under optimized conditions. Deuterium kinetic isotope effects and stoichiometric experiments provided insights into the C-H activation step and the intermediate involved in catalysis. The results support kinetic control of C-H activation as the origin of meta-selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Eunjae Chung, Suho Kim, Amitava Rakshit, Pargat Singh, Jaewook Park, Taejoo Jeong, In Su Kim
Summary: In this study, the rhodium(III)-catalyzed C8-spiroannulation of 1-aminonaphthalenes with maleimides is investigated. The resulting C8-alkenylated 1-aminonaphthalenes can further react with nucleophilic 1-amino groups through intramolecular aza-Michael reaction, leading to the formation of spirofused tetracyclic frameworks. This method demonstrates a broad substrate scope and compatibility with various functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
David Savary, Olivier Baudoin
Summary: C-H activation-based ring-forming methods are powerful for constructing complex molecular structures, especially useful for synthesizing chiral polycyclic aromatic hydrocarbons and other important organic electronic materials. A new enantioselective synthesis method using Pd-catalyzed C(sp(2))-H arylation protocol has been described, delivering diverse polycyclic compounds with high yield and good to excellent enantioselectivity, with investigation into their chiroptical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Chikako Matsuda, Ryo Igarashi, Hiroshi Katagiri, Takashi Murase
Summary: This study demonstrates that tri- and tetra-fluorinated [7]helicenes are photosensitive and undergo a double fluorine atom transfer. Furthermore, the transferred product undergoes a skeletal transformation on silica gel. These findings support the generation of a highly reactive cationic electrophilic intermediate in the successive transformations involving fluorine atoms.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Yi Luo, Yang-Hao Zeng, Lin Dong
Summary: Efficacious access to build fluorovinyl isoquinolines has been achieved through Rh(III)-catalyzed C-H functionalization between oxadiazoles and difluoromethylene alkynes with excellent chemoselectivity and regioselectivity. This protocol presents a practical method to install the fluorovinyl motif in the expected position of isoquinoline frameworks with wide functional group compatibility.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Rohit Sarthi, Rohit Kumar, Tamanna Sharma, Upendra Sharma
Summary: In this study, a concise Rh(III)-catalyzed C(sp3)-H alkylation of 8-methylquinolines with oxabenzonorbornadiene scaffolds and other strained olefins was presented. The developed catalytic methodology exhibits key features such as the retention of the oxabenzonorbornadiene skeleton, broad substrate scope, and wide-ranging functional group tolerance. Mechanistic studies revealed that the reaction proceeds through a non-radical pathway, with the five membered rhodacycle serving as the key intermediate. This is the first report on the C(sp3)-H alkylation of 8-methylquinolines with strained oxabenzonorbornadiene scaffolds (with ring retention).
Article
Chemistry, Multidisciplinary
Amrita Das, Naoto Chatani
Summary: The Rh-catalyzed C-H alkylation of benzylamines with alkenes using a picolinamide derivative as a directing group was successfully achieved under flow conditions with both Rh(i) and Rh(ii) complexes serving as active catalysts. Deuterium labelling experiments indicated a potential carbene mechanism for this reaction. The flow process demonstrated advantages over batch processes in this study.
Article
Chemistry, Organic
Shravani Battula, Hemalatha Bukya, Kunta Chandra Shekar, Kiranmai Nayani
Summary: A Rh(III)-catalyzed annulation was achieved between 2-arylimidazo[1,2-a]pyridines and p-quinols, leading to the formation of bridged heterocycles with three contiguous stereocenters via a twofold conjugate addition. The cascade reaction showed diastereoselectivity and proceeded through a sequential Rh-catalyzed ortho C(sp(2))-H functionalization of the aryl group of imidazo[1,2-a]pyridine with p-quinol, followed by an intramolecular conjugate addition, to produce a series of diverse and novel bridged heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Seongho Jin, Jinwoo Kim, Dongwook Kim, Jung-Woo Park, Sukbok Chang
Summary: In this study, a Rh-catalyzed C-H acyloxylation under mild electrolytic conditions was developed, with anodic oxidation of a key rhodacyclic carboxylate intermediate enabling the product-releasing C-O bond-forming reductive elimination process. The accumulation of carboxylate near the electrode surface further induced the desired C-O bond formation, allowing ambient catalytic C-H oxygenation using stoichiometric amounts of readily accessible carboxylic acid coupling partners.
Article
Chemistry, Multidisciplinary
Anurag Singh, Rahul K. Shukla, Chandra M. R. Volla
Summary: In this study, a novel nonoxidative [5 + 1] annulation reaction was reported. By using Rh(III) catalyst, 2-alkenylanilides and allenyl acetate were selectively reacted to obtain 1,2-dihydroquinoline derivatives. The reaction involves a series of steps including activation, insertion, elimination, and cyclization, achieving the construction of compounds. The method has a wide range of applications and can be used for functionalization of natural products.
Article
Chemistry, Multidisciplinary
Ronan Rocaboy, David Dailler, Florian Zellweger, Markus Neuburger, Christophe Salome, Eric Clot, Olivier Baudoin
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
Article
Chemistry, Multidisciplinary
Francesco Foschi, Torsten Roth, Markus Enders, Hubert Wadepohl, Eric Clot, Lutz H. Gade
CHEMICAL COMMUNICATIONS
(2018)
Article
Chemistry, Multidisciplinary
Lukas S. Merz, Hubert Wadepohl, Eric Clot, Lutz H. Gade
Article
Chemistry, Physical
Duo Wei, Omar Sadek, Vincent Dorcet, Thierry Roisnel, Christophe Darcel, Emmanuel Gras, Eric Clot, Jean-Baptiste Sortais
JOURNAL OF CATALYSIS
(2018)
Article
Chemistry, Organic
Yujia Liu, Julien Berges, Yassir Zaid, Fouad Ouazzani Chahdi, Arie Van der Lee, Dominique Harakat, Eric Clot, Florian Jaroschik, Marc Taillefer
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Physical
David Balcells, Eric Clot, Stuart A. Macgregor, Feliu Maseras, Lionel Perrin
Article
Chemistry, Multidisciplinary
Nele Konrad, Darya Meniailava, Irina Osadchuk, Jasper Adamson, Mohammed Hasan, Eric Clot, Riina Aav, Victor Borovkov, Dzmitry G. Kananovich
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2020)
Article
Chemistry, Physical
Yorck Mohr, Marc Renom-Carrasco, Clement Demarcy, Elsje Alessandra Quadrelli, Clement Camp, Florian M. Wisser, Eric Clot, Chloe Thieuleux, Jerome Canivet
Article
Chemistry, Inorganic & Nuclear
Soukaina Bennaamane, Maria F. Espada, Ikram Yagoub, Nathalie Saffon-Merceron, Noel Nebra, Marie Fustier-Boutignon, Eric Clot, Nicolas Mezailles
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2020)
Article
Multidisciplinary Sciences
Irina Osadchuk, Nele Konrad, Khai-Nghi Truong, Kari Rissanen, Eric Clot, Riina Aav, Dzmitry Kananovich, Victor Borovkov
Summary: The complexation of BTI with bis(ZnOEP) forms a 1:2 host-guest complex, where BTI molecules coordinate to the zinc ions of the porphyrin subunits of the host. Experimental and computational results agree, and the CD spectrum is shown to be sensitive to the spatial arrangement of the porphyrin subunits.
Article
Chemistry, Physical
Irina Osadchuk, Riina Aav, Victor Borovkov, Eric Clot
Summary: In this study, the influence of various controlling factors on electronic circular dichroism (ECD) spectra was investigated by modeling sixteen different zinc porphyrins using DFT and TD-DFT approaches. The factors mainly affected the excitation energy of electronic transitions and their intensity.
Article
Chemistry, Inorganic & Nuclear
Ramaraj Ayyappan, Koushik Saha, Mary Grellier, Eric Clot, Laure Vendier, Sundargopal Ghosh, Sylviane Sabo-Etienne, Sebastien Bontemps
Summary: A series of anionic ruthenium pentahydride complexes with different structural features were synthesized and characterized using various techniques. X-ray diffraction provided snapshots of some isomeric structures, while NMR analysis showed these complexes exhibited highly dynamic behavior. The rapid H-D exchange between Ru-H and D-2 was attributed to Li-Ru interactions in the absence of crown-ether.
Article
Chemistry, Multidisciplinary
Anais Coffinet, David Specklin, Quentin Le De, Soukaina Bennaamane, Luna Munoz, Laure Vendier, Eric Clot, Nicolas Mezailles, Antoine Simonneau
Summary: Two different dinitrogen-derived molybdenum nitrido complexes with different geometries, ligand spheres, and oxidation states were found to bond with the strong Lewis acid B(C6F5)(3) through their N ligand. The stable adducts were then used for heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C6F5)(2) in a frustrated Lewis pair-type manner. The results showed successful Si-H bond activation and substitution of B(C6F5)(3) by HB(C6F5)(2), depending on the nature of the nitrido complex. No B-H bond splitting was observed. The computed thermodynamics by DFT were consistent with the experimental outcomes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jian Yang, Veronica Postils, Michael Lipschutz, Meg Fasulo, Christophe Raynaud, Eric Clot, Odile Eisenstein, T. Don Tilley
Article
Chemistry, Physical
Irina Osadchuk, Victor Borovkov, Riina Aav, Eric Clot
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2020)
