Article
Chemistry, Organic
Yang Gao, Yushan Cui, Yanping Huo, Jinhong Chen, Minwei She, Xianwei Li, Qian Chen, Xiao-Qiang Hu
Summary: A nickel-catalyzed polarity-reversed hydroamination of olefins has been developed, providing a convenient route to N-alkyl-2-aminobenzophenones intermediates. This method is compatible with a wide range of olefins and anthranils, delivering the desired amines in high yields, making it applicable for organic synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Jorge Escorihuela, Agusti Lledos, Gregori Ujaque
Summary: Hydroamination, the addition of an N-H bond across a C-C multiple bond, is a reaction with significant synthetic potential. This review focuses on achieving anti-Markovnikov regioselectivity in intermolecular hydroaminations of terminal alkynes and alkenes. The mechanisms and factors that favor anti-Markovnikov regioselectivity are discussed, along with alternative pathways and different catalysts.
Article
Chemistry, Physical
Srimanta Manna, Joannes Peters, Aitor Bermejo-Loïpez, Fahmi Himo, Jan-E. Backvall
Summary: The mechanism of dehydrogenation of amines catalyzed by (cyclopentadienone)iron carbonyl complexes was studied using KIE measurements, intermediate isolation, and density functional theory calculations. The intermediates of (cyclopentadienone)iron-amine were isolated and characterized, and the KIEs observed supported a stepwise dehydrogenation process. Density functional calculations confirmed a stepwise mechanism involving hydride transfer and proton transfer steps.
Article
Chemistry, Multidisciplinary
Kentaro Yamakawa, Kana Sakamoto, Takahiro Nishimura
Summary: The enantioselective addition of an imide N-H bond to alkenes has been achieved using a cationic iridium catalyst. Bulky diphosphine ligands were crucial for the reaction, and various substrates including styrene derivatives, allylsilanes, and norbornene gave chiral adducts with high enantioselectivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kentaro Yamakawa, Kana Sakamoto, Takahiro Nishimura
Summary: In this study, enantioselective addition of an imide N-H bond to alkenes was achieved using a cationic iridium catalyst. Bulky diphosphine ligands played a crucial role in the reaction. Various substrates, such as styrene derivatives, allylsilanes, and norbornene, reacted well with alkenes to afford chiral adducts with high enantioselectivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yaoyu Liang, Jie Luo, Yael Diskin-Posner, David Milstein
Summary: Utilization of main-group metals as alternatives to transition metals in homogeneous catalysis is a hot research area. However, their application in catalytic hydrogenation is less common due to the difficulty in heterolytic cleavage of the H-H bond. Employing metal-ligand cooperation highly enhances the H-2 activation process, offering an efficient approach for the hydrogenation of unsaturated molecules catalyzed by main-group metals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yaoyu Liang, Jie Luo, Yael Diskin-Posner, David Milstein
Summary: The utilization of main-group metals in homogeneous catalysis as alternatives to transition metals has gained much attention recently. However, their application in catalytic hydrogenation is limited due to the difficulty in cleaving the H-H bond. In this study, new magnesium pincer complexes were developed and employed for the homogeneous catalytic hydrogenation of unsaturated molecules, showing promising results and expanding the scope of main-group metal catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chaosheng Luo, Juan V. Alegre-Requena, Stephen J. Sujansky, Spencer P. Pajk, Liliana C. Gallegos, Robert S. Paton, Jeffrey S. Bandar
Summary: This study investigates the mechanism of nucleophilic addition of alcohols to simple alkenes, revealing the influence of alcohol stoichiometry on reaction rate and proposing a new solution. The improved method does not require excess alcohol, expands the substrate scope, and utilizes more practical catalyst systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Kadiyala Sagar, Tapas R. Pradhan, Abdikani Omar Farah, Henry R. Wise, Bhailal C. Merja, Malempati Srimannarayana, Paul Ha-Yeon Cheong, Jin Kyoon Park
Summary: The assistance of 1,1,1,3,3,3-hexafluoro-2-propanol enables the metal-free synthesis of 1,3-diamines via regioselective intermolecular interception of amines. N-chemoselectivity and regioselectivity are achieved for a wide range of substrates. Mechanistic studies and computational calculations provide insights into the reaction pathway and selectivity control.
Article
Chemistry, Multidisciplinary
Xiaoyong Du, Ye Xiao, Yuhong Yang, Ya-Nan Duan, Fangfang Li, Qi Hu, Lung Wa Chung, Gen-Qiang Chen, Xumu Zhang
Summary: The enantioselective hydrogenation of cyclic and acyclic tetrasubstituted alpha, beta-unsaturated carboxylic acids via cobalt(II) catalysis demonstrated broad substrate scope and excellent enantiocontrol. Combined experimental and computational mechanistic studies supported a Co-II catalytic cycle involving migratory insertion and sigma-bond metathesis processes, with enantioselectivity possibly originating from the steric effect between the phenyl groups of the ligand and the substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Akshi Tyagi, Sunita Mondal, Anmol, Vikas Tiwari, Tarak Karmakar, Subrata Kundu
Summary: The research demonstrates that the hydroamination of electron-deficient olefins can be efficiently carried out using the (CAAC)Cu-Cl catalyst at room temperature and under an open atmosphere, and the catalyst also shows excellent efficiency in the hydroaryloxylation and hydroalkoxylation of alkenes. Detailed computational studies reveal that the reaction proceeds via either a four-membered or a six-membered cyclic transition state containing the copper ion.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Peng-Fei Yang, Jian-Xing Liang, Han -Tong Zhao, Wei Shu
Summary: In this study, a straightforward method to access enantioenriched 1,n-diamines containing a chiral alpha-branched aliphatic amine is achieved through Ni-catalyzed asymmetric hydroamination. This method delivers good yields and excellent enantioselectivities with diverse substitution patterns, and exhibits excellent functional group tolerance.
Article
Chemistry, Organic
Purushothaman Yamuna, Rose Mary Philip, Gopinathan Anilkumar
Summary: This study reviews the progress of nickel-catalyzed hydroamination reactions, including both homogeneous and heterogeneous catalytic systems. Nickel complexes have shown low cost, non-toxicity, and unique reactivity in this reaction.
Article
Chemistry, Multidisciplinary
Mandapati Bhargava Reddy, Sakthivel Prabhu, Ramasamy Anandhan
Summary: An unprecedented reductive hydroamidative/hydroquinazolinative cascade cyclization of o-alkynylated derivatives was achieved via proton-coupled electron transfer (PCET) under electrolysis. In a single step, the rapid assembly of isoindolinones and novel isoindole-fused quinazolinones were achieved through electrolysis by the hydroamidation of amidyl/quinazolinone aminyl radicals with C-C triple bond addition via 5-exo-dig cyclization followed by olefinic reduction without external reductants. Control and cyclic voltammetry experiments support a mechanistic explanation of the electrochemical cascade, and these experiments indicate that the electrolyte is the source of hydrogen for the olefin reduction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Huanran Miao, Meihui Guan, Tao Xiong, Ge Zhang, Qian Zhang
Summary: In this research, a Co-catalyzed asymmetric hydroamination reaction using commercially accessible secondary amines was developed, allowing for the efficient synthesis of alpha-chiral tertiary amines with good enantioselectivities. Mechanistic studies revealed that the reaction involves CoH-mediated hydrogen atom transfer and a pivotal catalyst-controlled S(N)2-like reaction pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Pablo Gomez-Orellana, Agusti Lledos, Gregori Ujaque
Summary: The Buchwald-Hartwig amination of arylhalides with the Pd-Josiphos complex using ammonia as a reactant is a useful process for primary amine synthesis. Density-functional theory calculations were used to examine the reaction mechanism, revealing the importance of the chelate phosphine ligand and base in the process. The study allowed for the proposal of a complete reaction mechanism for the Pd-catalyzed C-N coupling reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Gantulga Norjmaa, Jean-Didier Marechal, Gregori Ujaque
Summary: The reductive elimination reactions of Pt and Au were studied, revealing no additional solvent molecules inside the metal cage, and indicating that encapsulation has a more significant effect on reducing energy barriers.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Medicinal
Gantulga Norjmaa, Pietro Vidossich, Jean-Didier Marechal, Gregori Ujaque
Summary: The study reports the calculation of the Gibbs energy barrier and Gibbs binding energy using explicit solvent molecular simulations for [Ga4L6](12-) metallocage encapsulating a series of cationic molecules. The Gibbs energy barrier for encapsulation was estimated using umbrella sampling simulations. The Gibbs binding energy values were computed using the attach-pull-release method. Results show sensitivity on force field parameters, specifically on atomic charges, where higher accuracy is obtained when charges are derived from implicit solvent quantum chemical calculations. Correlation analysis identified indicators for binding affinity trends.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Chemistry, Multidisciplinary
Guillermo Marcos-Ayuso, Agusti Lledos, Juan A. Casares
Summary: Experimental studies and calculations show that the oxidative addition of aryl halides to copper complexes follows different paths depending on the nature of the halogen. For bromine, a concerted addition leads to the formation of a C-C coupled product, while for iodine, a different complex is formed and an elimination reaction occurs.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Jose-Emilio Sanchez-Aparicio, Giuseppe Sciortino, Eric Mates-Torres, Agusti Lledos, Jean-Didier Marechal
Summary: This study explores the challenges and solutions in molecular modelling applications in metalloenzyme design. By incorporating new tools in multiscale strategies, particularly substrate diffusion exploration, a deeper understanding of metal-mediated binding and catalytic geometry can be achieved. Using various variants of an artificial Rh-2-based cyclopropanase as examples, DFT calculations and molecular dockings reveal the catalytic mechanisms controlled by the protein.
FARADAY DISCUSSIONS
(2022)
Article
Chemistry, Applied
Gantulga Norjmaa, Gregori Ujaque, Agusti Lledos
Summary: The use of solvent effects in computational modeling of homogeneous catalysis is essential for capturing accurate mechanistic details. While continuum solvent models are commonly used, explicit solvent models are often necessary to provide a more detailed and accurate representation, leading to improved mechanistic understanding of reactions. Through selected examples, this article highlights the limitations of continuum solvent models and the benefits of incorporating explicit solvent molecules in quantum mechanical descriptions.
TOPICS IN CATALYSIS
(2022)
Correction
Chemistry, Physical
Fadri Christoffel, Nico V. Igareta, Michela M. Pellizzoni, Laura Tiessler-Sala, Boris Lozhkin, Daniel C. Spiess, Agusti Lledos, Jean-Didier Marechal, Ryan L. Peterson, Thomas R. Ward
Article
Chemistry, Multidisciplinary
Gantulga Norjmaa, Fahmi Himo, Jean-Didier Marechal, Gregori Ujaque
Summary: The mechanism of the Nazarov cyclization was investigated using computational methods in both solution and within a supramolecular organometallic cage. It was found that the reaction can proceed at neutral pH in the presence of the cage, eliminating the need for acidic conditions. The study provides valuable insights into the impact of the cage on the reaction steps and identifies key catalytic steps.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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
Laura Tiessler-Sala, Giuseppe Sciortino, Lur Alonso-Cotchico, Laura Masgrau, Agusti Lledos, Jean-Didier Marechal
Summary: In this study, computational techniques were used to investigate and compare the mechanisms of two heme-binding systems. The results revealed different heme-binding mechanisms between the two systems, with one system having similar conformational spaces in the absence and presence of heme, while the other system only exhibited similar conformations to the holo form when heme was bound. This study highlights the diversity of molecular mechanisms of heme-binding.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Andres M. Alvarez-Constantino, Andrea Alvarez-Perez, Jesus A. Varela, Giuseppe Sciortino, Gregori Ujaque, Carlos Saa
Summary: A new Ru-catalyzed intramolecular oxidative amida-tion reaction has been developed, which efficiently synthesizes medium-sized euro- and zeta- lactams but not common t5-lactams. DFT studies reveal the important role of chain length between the amine and alkyne functionalities in this reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Cintya Pinilla, Vanesa Salamanca, Agusti Lledos, Ana C. Albeniz
Summary: Metal-catalyzed C-H functionalizations on the aryl ring of anilines usually require cumbersome N-protection-deprotection strategies for chemoselectivity. In this study, we demonstrate a Pd-catalyzed direct C-H arylation of unprotected anilines with no competition from N-arylation product. The ligand [2,2'-bipyridin]-6(1H)-one drives the chemoselectivity by kinetic differentiation in the product-forming step while aiding in the C-H cleavage step. The deprotonation of the NH moiety in an anionic intermediate favors regioselectivity towards ortho substitution.
Review
Chemistry, Multidisciplinary
Jorge Escorihuela, Agusti Lledos, Gregori Ujaque
Summary: Hydroamination, the addition of an N-H bond across a C-C multiple bond, is a reaction with significant synthetic potential. This review focuses on achieving anti-Markovnikov regioselectivity in intermolecular hydroaminations of terminal alkynes and alkenes. The mechanisms and factors that favor anti-Markovnikov regioselectivity are discussed, along with alternative pathways and different catalysts.
