Article
Chemistry, Organic
Jiangkun Huang, Rui Zhang, Xiuli Wu, Guangbin Dong, Ying Xia
Summary: In this study, a Rh-catalyzed intramolecular one-carbon homologation of unstrained aryl ketones was developed through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C-C activation. The reaction provides a unique approach to access various substituted 1-indanones.
Article
Chemistry, Applied
Juan Diego Pizarro, Lucia Moran-Gonzalez, Ivan Gonzalez-Fernandez, Feliu Maseras, Manuel R. Fructos, Pedro J. Perez
Summary: Copper catalysts containing ADAP ligand selectively functionalize unprotected indoles at the C3-H position through carbene transfer, without altering the N-H bond. Mechanistic studies, including DFT calculations, propose two competitive pathways that do not involve the formation of cyclopropane intermediates, contrasting with previous reports.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Peil, Alejandro Gutierrez Gonzalez, Markus Leutzsch, Alois Fuerstner
Summary: This study demonstrates the highly unorthodox hydrogenation transformation of an internal alkyne using [Cp*RuCl](4) as a precatalyst. The reaction shows regioselectivity and forms vinyl carbene complexes with various binding modes as intermediates. The access to spirocyclic and bridged ring systems through this reaction is of great significance in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jake R. Jagannathan, Karina Targos, Annaliese K. Franz
Summary: Carbene insertion into Si-H bonds of polyhedral oligomeric silsesquioxanes (POSS) using dirhodium(II) carboxylates as catalysts allows for the synthesis of highly functionalized siloxane nanomaterials. This method results in the production of 20 new POSS compounds with diverse structures, containing both ester and aryl groups for further derivatization. The transformations of aryl(ester)-functionalized POSS compounds, including ester hydrolysis and Suzuki-Miyaura cross-coupling, demonstrate the versatility and potential applications of these highly functionalized substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Xu Liu, Limin Wang, Hao-Yang Wang, Jianwei Han
Summary: In this study, an efficient site-selective O-arylation method for complex arenes involving intramolecular aryl rearrangement is presented. The reaction is facilitated by diaryliodonium salts bearing vicinal trifluoromethanesulfonate (OTf) groups. The procedure starts with selective C-H bond activation of arenes, followed by nucleophilic aromatic substitution (SNAr) to convert them into diaryl ethers. This synthetic method successfully provides complex diaryl ether derivatives, demonstrating its practicality in the diversification of functionalized arenes and pharmaceutical agents.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Lei Gao, Sheng Liu, Zi-Chao Wang, Yongjun Mao, Shi-Liang Shi
Summary: The study presents a ligand- and additive-free CuCl2-catalyzed highly selective para-C-H carbene insertion reaction, which can produce a variety of 1,1-diarylacetates with high yields and excellent selectivity.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Corentin Rumo, Alina Stein, Juliane Klehr, Ryo Tachibana, Alessandro Prescimone, Daniel Haussinger, Thomas R. Ward
Summary: The selective functionalization of organic compounds is a versatile tool, and artificial metalloenzymes offer an ideal means to modify inert motifs. In this study, quantum mechanics/molecular mechanics simulations were used to identify target residues for genetic optimization of the artificial metalloenzyme. Double-saturation mutagenesis provided detailed insight on the activity and selectivity, leading to the development of artificial metalloenzymes that efficiently catalyze the formation of β- and γ-lactams.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Dhanaji Jawale, Frederic Fossard, Frederic Miserque, Valerie Geertsen, Anne-Lucie Teillout, Pedro de Oliveira, Israel M. Mbomekalle, Edmond Gravel, Eric Doris
Summary: In this study, electroactive hybrid nanomaterials were assembled by non-covalent, layer-by-layer deposition of tungsten-based polyoxometalates on carbon nanotubes. Chemical functionalization allowed for the homogeneous coverage of polyoxometalates on the nanotubes. Electrochemical characterization highlighted the positive contribution of the nanotube platform to the stability and catalytic performance of immobilized POM species when applied to the hydrogen evolution reaction.
Article
Chemistry, Multidisciplinary
Hang Li, Na Li, Jinghao Wu, Tianyang Yu, Ran Zhang, Li-Ping Xu, Hao Wei
Summary: In this study, a method for direct insertion of an intramolecular nitrogen atom into an aromatic C-C bond was described. Carbamoyl azides were activated by a Rh catalyst and inserted directly into the C-C bond of an arene ring to produce fused azepine products. The use of a paddlewheel dirhodium complex effectively inhibited the undesired C-H insertion. Density functional theory calculations were used to elucidate the reaction mechanism and chemoselectivity of the Rh-catalyzed reactions. The resulting fused azepine products are highly stable and can be further diversified.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Dharmendra Kumar, Malleswara Rao Kuram
Summary: Easy access to divergent products through chemoselective copper-catalyzed carbene insertion onto N-H bonds of tryptamine derivatives is achieved by varying the nucleophilicity of the aliphatic NH and electron-donating or electron-withdrawing groups. The reaction provides N-H insertion products with broad substrate scope and good yields.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Lucas Vidal, Pan -Pan Chen, Eva Nicolas, Andrew Hackett, Craig M. Robertson, Kendall N. Houk, Christophe Aissa
Summary: The iridium-catalyzed intramolecular cyclopropanation of alpha-carbonyl sulfoxonium ylides (SY) in the presence of a chiral diene is reported with high yield (up to 96%) and enantioselectivity (98%). Density functional theory calculations suggest that the re face of the olefin prefers to attack an iridium carbene intermediate in an asynchronous concerted step independent of the geometry of the olefin.
Article
Chemistry, Physical
Takuya Murai, Wenjie Lu, Toshifumi Kuribayashi, Kazuhiro Morisaki, Yoshihiro Ueda, Shohei Hamada, Yusuke Kobayashi, Takahiro Sasamori, Norihiro Tokitoh, Takeo Kawabata, Takumi Furuta
Summary: D-2-symmetric dirhodium(II) carboxylate catalysts bearing axially chiral binaphthothiophene delta-amino acid derivatives have been developed, with conformational control supported through chalcogen-bonding interactions providing well-defined and uniform asymmetric environments. These complexes act as asymmetric catalysts for stereoselective intramolecular C-H insertion to yield various cis-alpha,beta-diaryl gamma-lactones, with high diastereo- and enantioselectivities, and can also be used for short total syntheses of naturally occurring gamma-lactones.
Article
Chemistry, Applied
Ilaria Barlocco, Silvio Bellomi, Juan J. Delgado, Xiaowei Chen, Laura Prati, Nikolaos Dimitratos, Alberto Roldan, Alberto Villa
Summary: Palladium nanoparticles were deposited on oxygen and phosphorous functionalized carbon nanofibers to investigate the support-metal effect on the formic acid decomposition reaction. Characterization and evaluation of catalytic performance confirmed the superior properties of the catalysts in both functionalized materials. Density functional theory simulations further provided insights into the interaction between Pd clusters and different support surfaces.
Article
Chemistry, Multidisciplinary
Kevin Breitwieser, Fabian Dankert, Annette Gruenwald, Paula R. Mayer, Frank W. Heinemann, Dominik Munz
Summary: This study reports C-C insertion reactions of a 12-electron palladium(0) surrogate stabilized by a cyclic(alkyl)(amino) carbene (CAAC) ligand. The reactions proceed quantitatively at or below room temperature, outlining perspectives for C-C bond functionalization catalysis.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Elena Borrego, Pedro J. Perez, Ana Caballero
Summary: The copper complex Tp((CF3)2,Br)Cu(NCMe) efficiently catalyzes the aziridination of olefins in water using PhI=NTs as the nitrene source, with similar activity to that observed in dichloromethane. No specific modification of catalyst or substrates is needed, and additional phase transfer catalyst is not required.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Anabel M. Rodriguez, Jorge Perez-Ruiz, Francisco Molina, Ana Poveda, Raul Perez-Soto, Feliu Maseras, M. Mar Diaz-Requejo, Pedro J. Perez
Summary: This paper describes the direct functionalization of Si-H bonds using nitrene insertion methodology. It was found that a copper(I) complex with a trispyrazolylborate ligand can catalyze the transfer of a nitrene group from PhI=NTs to the Si-H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si-NH moieties. The process is also tolerant of other functionalities in the substrate, such as multiple C-H bonds and alkynyl and vinyl moieties directly bonded to the silicon center. Density functional theory calculations provide a mechanistic interpretation involving Si-H homolytic cleavage and subsequent rebound to the Si-centered radical.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jose Maria Munoz-Molina, Daniel Bafaluy, Ignacio Funes-Ardoiz, Adiran de Aguirre, Feliu Maseras, Tomas R. Belderrain, Pedro J. Perez, Kilian Muniz
Summary: In this study, we report a new method for the synthesis of pyrrolidines and piperidines via intramolecular C-H amination, and investigate the mechanistic pathway, revealing a key fluorinated copper(II) complex. The effects of catalyst ligand and substrate halide were explored from experimental and computational perspectives.
Article
Chemistry, Physical
Juan Diego Pizarro, Inga L. Schmidtke, Ainara Nova, Manuel R. Fructos, Pedro J. Perez
Summary: The complete regioselective incorporation of carbene units to nonactivated arene rings has been achieved using gold(I) catalysts and readily available, nonelaborated ethyl 2-phenyldiazoacetate as the carbene source, which is in contrast with previous examples that required highly modified diazo compounds.
Review
Chemistry, Inorganic & Nuclear
Elena Borrego, Ana Caballero, Pedro J. Perez
Summary: Micellar catalysis is a method that utilizes micelles as nanovessels for catalytic transformations, particularly in the catalytic functionalization of carbon-hydrogen bonds. By accumulating catalyst and reactants in high local concentrations, micelles enable reactions to occur under milder conditions compared to conventional organic solvents.
Article
Chemistry, Inorganic & Nuclear
Elena Borrego, Laura Tiessler-Sala, Jesus J. Lazaro, Ana Caballero, Pedro J. Perez, Agusti Lledos
Summary: The direct oxidation of benzene into phenol using a copper complex catalyst is investigated. The dinuclear species Tp(Br3)Cu(II)(mu-O-center dot)(mu-OH)Cu(II)Tp(Br3) is proposed as the key structure responsible for activating the arene C-H bond leading to phenol formation.
Article
Chemistry, Inorganic & Nuclear
Jorge Perez-Ruiz, Pedro J. Perez, M. Mar Diaz-Requejo
Summary: Complexes of [(NHC)MCl] (M = coinage metal) were investigated as catalysts for olefin aziridination reaction and showed moderate to high activity depending on the metal and olefin. Unlike commonly used copper catalysts with bi-, tri-, or tetradentate N-donor ligands, the monodentate C-donor ligands in these complexes have a remarkable effect on the reaction mechanism.
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Maria Alvarez, Francisco Molina, Pedro J. Perez
Summary: Control of regioselectivity in the functionalization of linear alkanes' C-H bonds can be achieved using silver complexes as catalysts. This alternative approach mainly relies on the choice of the diazo reagent to govern the regioselectivity, leading to functionalization at primary or secondary sites of the linear alkanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Editorial Material
Chemistry, Inorganic & Nuclear
Anne M. LaPointe, Pedro J. Perez
Article
Chemistry, Physical
Manuel R. Rodriguez, Anabel M. Rodriguez, Sara Lopez-Resano, Miquel A. . Pericas, M. Mar Diaz-Requejo, Feliu Maseras, Pedro J. Perez
Summary: In the context of copper-catalyzed nitrene transfer to olefins, this study challenges the general assumption that the X ligand is displaced from the coordination sphere. Through experiments with well-defined copper(I) complexes, it is demonstrated that the catalytic and mechanistic behavior depends on the presence or absence of the chloride ligand bonded to the metal center, with different turnover-limiting steps.
Article
Chemistry, Inorganic & Nuclear
Martina Casciotti, Guillermo Romo-Islas, Maria Alvarez, Francisco Molina, Jose Maria Munoz-Molina, Tomas R. Belderrain, Laura Rodriguez
Summary: This paper reports the synthesis and characterization of two dinuclear and five tetranuclear gold(I) complexes. The tetranuclear gold(I) complexes were obtained by reacting the dinuclear complexes with Ag salts, resulting in different terminal ancillary ligands and counter ions. The structures of the complexes were confirmed by single-crystal X-ray diffraction studies, and aurophilic interactions were observed in some of the complexes. The application of these gold(I) complexes as catalysts in a heteroarylation reaction was investigated, and the progress of the catalytic reaction was tracked using luminescence techniques.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Jonathan Martinez-Laguna, Andres Mollar-Cuni, David Ventura-Espinosa, Santiago Martin, Ana Caballero, Jose A. Mata, Pedro J. Perez
Summary: In this study, a novel strategy was developed to functionalize C-H bonds of cyclohexane and benzene with the assistance of nanoparticulated gold catalyst. The catalyst showed exceptional activity and recyclability.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Manuel R. Rodriguez, M. Mar Diaz-Requejo, Pedro J. Perez
Summary: In recent years, metal-nitrene-transfer reactions have made significant progress in expanding the synthesis scope of organic compounds through the use of copper or silver complexes as catalysts. This has allowed for the efficient synthesis of complex structures from relatively simple starting materials.
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
