Article
Chemistry, Multidisciplinary
Lijun Lu, Hao Li, Aiwen Lei
Summary: Oxidative cross-coupling reactions between two nucleophiles have become a significant tool in organic synthesis for constructing chemical bonds. This reaction model was discovered through the cross-coupling of two organometallic reagents and related mechanisms were revealed through the characterization of intermediates and study of reaction kinetics using operando spectroscopy. The reaction exhibits high atom and step economy, making it an ideal and economical process for synthesizing valuable chemicals.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jian Luo, Bo Hu, Wenda Wu, Maowei Hu, T. Leo Liu
Summary: This study reports a redox neutral electrochemical C(sp(2))-C(sp(3)) cross-coupling reaction conducted under ambient conditions using nonprecious metal catalysts. The reaction demonstrated good yields and a broad scope, with potential applications in pharmaceuticals and natural amino acid modification. The method, which proceeds through an unconventional radical transmetalation mechanism, is highly productive and expected to have widespread applications in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Chao-Jiu Long, Huan Cao, Ben-Kun Zhao, Yu-Fang Tan, Yan-Hong He, Chu-Sheng Huang, Zhi Guan
Summary: The enantioselective oxidative cross-coupling of secondary amines with ketones was achieved by combining the catalytic activity of lipase with electrosynthesis. This novel protocol allowed for the synthesis of 2,2-disubstituted 3-carbonyl indoles with a stereogenic quaternary carbon center in high yields and good enantio- and diastereoselectivities. The compatibility of hydrolase catalysis with electrosynthesis was demonstrated, highlighting the potential and mechanism of enzymatic electrosynthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Gregory A. Dawson, Ethan H. Spielvogel, Tianning Diao
Summary: Nickel-catalyzed radical reactions are important for the synthesis of noncanonical peptides and carbohydrates, and have potential applications in chemical biology studies and drug discovery. The understanding of each step involving radicals, including initiation, propagation, termination, and the nuances of kinetics, origins of selectivity, and ligand effects, is crucial for the development of these reactions.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Review
Chemistry, Multidisciplinary
Yaowen Liu, Pengfei Li, Yanwei Wang, Youai Qiu
Summary: Electrochemistry employs electrons as an efficient and sustainable alternative to chemical oxidants or reductants, and has gained popularity for selective organic synthesis. The combination of electrochemistry with readily available electrophiles has emerged as a viable method for constructing challenging C-C and C-heteroatom bonds. This mini-review provides a systematic summary of the recent advances in electroreductive cross-electrophile coupling (eXEC) reactions, focusing on aryl and alkyl organic (pseudo)halides, as well as small molecules such as CO2, SO2, and D2O.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zijian Zhong, Pan Xu, Jinfeng Ma, Aihua Zhou
Summary: A green electrochemical oxidative cross-coupling protocol has been developed for the generation of thiosulfonates and sulfonate esters using sodium arenesulfinates and thiophenols/phenols. The reactions utilize inorganic and non-toxic NaI as redox catalyst and supporting electrolyte at room temperature without the need for oxidant and base, providing good yields of products and tolerating broad substrate scope. Mechanistic studies revealed that the reactions proceed via a radical pathway for the formation of SO2-S and SO2-O bonds.
Article
Multidisciplinary Sciences
Wei Liu, Marissa N. Lavagnino, Colin A. Gould, Jesus Alcazar, David W. C. MacMillan
Summary: The S(H)2 mechanism has been utilized in the synthetic formation of organic molecules to create quaternary sp(3)-carbon centers. The mechanism involves distinguishing between primary and tertiary carbons to form S(H)2 bonds and generating radical classes simultaneously from abundant functional groups using photocatalysis.
Article
Chemistry, Physical
Taline Kerackian, Didier Bouyssi, Guillaume Pilet, Maurice Medebielle, Nuno Monteiro, Julien C. Vantourout, Abderrahmane Amgoune
Summary: This article describes the development and in-depth study of a cross-electrophile coupling of alkyl N-acyl imides with alkyl halides using nickel catalysis and electrochemistry. The method utilizes the stability and easy access of N-acyl imides to selectively synthesize dissymmetric dialkyl ketones. Mechanistic studies reveal the generation of alkyl radicals through single-electron oxidation of alkyl bromides by electrogenerated (bpy)Ni(I) species. The reaction of alkyl N-acyl imides with (bpy)Ni(0) and (bpy)Ni(I) species leads to Ni(II) acyl intermediates. A comprehensive mechanistic picture of this selective cross-electrophile coupling is achieved through these investigations.
Article
Chemistry, Multidisciplinary
Chen Zhu, Shao-Chi Lee, Haifeng Chen, Huifeng Yue, Magnus Rueping
Summary: This paper presents a reductive cross-coupling reaction between alpha-oxy halides generated from aldehydes and various C(sp(2))- and C(sp)-electrophiles, achieving the formation of protected alcohols and alpha-hydroxy ketones. The interchange of different catalytic strategies indicates underlying mechanistic similarities, with the generation of Ni-I intermediate proposed as a key point for ketyl radical formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xinyan Zhou, Jin Hao, Yilin Kong, Runsheng Xu
Summary: An iron-catalyzed cascade reaction allows for the synthesis of various derivatives under mild conditions, providing an economical approach for C(sp(3))-Se bond formation starting from 1,2,3,4-tetrahydroisoquinolines and 2-hydroselenobenzoic acids.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Evgeniy O. Bortnikov, Sergey N. Semenov
Summary: The coupling of transition-metal to photoredox catalytic cycles through single-electron transfer steps has become a powerful tool in the development of catalytic processes. AC-assisted Ni-catalyzed reactions showed higher yields and selectivity, and mechanistic studies highlighted the importance of both reduction and oxidation processes in these reactions. The AC assistance appears to be well-suited for catalytic cycles involving reductive elimination or oxidative addition as a limiting step.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jing Cao, Antonia Seitz, Jose A. Forni, Anastasios Polyzos, David W. Lupton
Summary: This article reports on a reaction design that avoids the facile oxidation of phosphine organocatalyst and combines traditional nucleophilic phosphine organocatalysis with photoredox catalysis to enable Giese coupling with ynoates. The approach exhibits good generality, and its mechanism is supported by cyclic voltametric, Stern-Volmer quenching, and interception studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: In this study, a nickel-catalyzed, three-component reductive protocol for group 14 element hetero-difunctionalization of 1,3-enynes using electrochemistry is described. The method is mild, selective, and general, allowing for the silyl-, germanyl-, and stannyl-alkylation of enynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Guoqing Yang, Yanwei Wang, Youai Qiu
Summary: A nickela-electrocatalyzed cross-electrophile coupling of aryl aziridines and aryl bromides has been developed to access synthetic useful beta-arylethylamines under mild and sustainable electrochemical conditions. This protocol exhibits excellent chemo- and regioselectivity, broad substrate scope, and good functional group compatibility. Mechanistic studies have confirmed that the observed regioselectivity and reactivity are due to the electro-induced ring-opening of aziridines to generate a benzyl radical intermediate as the active species. Furthermore, this strategy enables the cross-coupling with CO2 to access beta-amino acids under mild conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Qi-Ying Zhang, Lu-Xin Li, Song-Lin Wang, Jing Ma, Hai-Ming Guo
Summary: An electrochemically-driven organocatalytic enantioselective oxidative coupling of tetrahydroisoquinolines and acrylaldehyde was developed, leading to various chiral C1-alkenyl tetrahydroisoquinolines derivatives with yields of 69-86% and er of 93:7-96:4. This synthetic route offers access to various optically active C1-substituted tetrahydroisoquinolines derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yongxiang Zheng, Baptiste Moegle, Santanu Ghosh, Anna Perfetto, Davide Luise, Ilaria Ciofini, Laurence Miesch
Summary: A copper-mediated coupling reaction between ynamides and diazo-compounds to produce N-allenamides has been reported, providing a facile and rapid access to terminal N-allenamides with wide functional group compatibility on the nitrogen. This method was successfully applied to the synthesis of fluorine-substituted N-allenamides, which are important building blocks in various fields. DFT calculations provided insights into the mechanism involved in this reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Eric Bremond, Marika Savarese, Nadia Rega, Ilaria Ciofini, Carlo Adamo
Summary: By using different density functional approximations, we reconstructed the free energy profiles along reaction pathways and compared the computed barrier heights of proton transfer reactions using two different methods. The results show that the choice of density functional has a significant impact on the computed results, with local density functionals often underestimating the barrier heights.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Feven Alemu Korsaye, Aurelien de la Lande, Ilaria Ciofini
Summary: This paper presents a density-based method for describing and diagnosing the electronic density evolution in real-time time-dependent density functional theory simulations of a family of organic molecules. By computing charge transfer distance and diagnostic indices, the redistribution of density can be analyzed, and artificial factors in the simulations can be identified.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Davide Luise, Massimo Christian D'Alterio, Giovanni Talarico, Ilaria Ciofini, Frederic Labat
Summary: The absorption spectra of polymers derived from different positions of phenylenediamines were simulated using DFT calculations and TD-DFT simulations. The results were compared with solvated oligomers extracted from periodic structures. The study showed that for ortho- and para-phenylenediamines, modeling solvated dimers already achieved agreement with experimental data, while for meta-phenylenediamine, the inclusion of long-range electrostatic effects is necessary.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Physical
M. E. Sandoval-Salinas, E. Bremond, A. J. Perez-Jimenez, C. Adamo, J. C. Sancho-Garcia
Summary: A family of non-empirical double-hybrid density functionals based on Perdew-Burke-Ernzerhof (PBE) exchange and correlation functionals is utilized to calculate the excitation energies of linear and cyclic acenes. The calculated energies for different states are compared with experimental results and other double-hybrid expressions. The study demonstrates that these non-empirical functionals outperform hybrid functionals and provide competitive results.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Maciej Spiegel, Carlo Adamo
Summary: Photosensitizers with the Ru(II)-polypyridyl complex structure have shown potential as photodynamic therapy agents for treating neoplasms, but their poor solubility has been a challenge. This study investigates the use of a polyamine macrocycle ring as a solution to improve solubility. The results suggest that protonation of amine groups enhances reactivity, but complexation weakens the desired photoactivity.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Jun Su, Davide Luise, Ilaria Ciofini, Frederic Labat
Summary: We investigate the properties of different bulk MAPbX3 perovskite systems and heterointerface models between MAPI and TiO2, which are key components of perovskite solar cells. Using a combination of periodic and non-periodic calculations, we model the geometric, electronic, and optical properties of these systems and find that they have favorable features for solar devices. Our computational approach proves to be reliable and cost-effective for studying materials related to photovoltaic applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Lorenzo Briccolani-Bandini, Eric Bremond, Marco Pagliai, Gianni Cardini, Ilaria Ciofini, Carlo Adamo
Summary: In this study, the double proton transfer (PT) reaction in the complex molecule [2,2'-bipyridyl]-3-3'-diol was explored, revealing the coupling of proton movements with significant rearrangement of the electronic structure. The reaction could occur simultaneously (concerted) or sequentially (stepwise), with the characteristics of the stepwise PT depending on the chosen exchange-correlation functionals. The potential energy surface (PES) and free-energy surface (FES) were analyzed using density functional theory, showing variations in the stepwise mechanism and the presence of stable intermediates and transition states.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Maryam Mansoori Kermani, Hanwei Li, Alistar Ottochian, Orlando Crescenzi, Benjamin G. Janesko, Giovanni Scalmani, Michael J. Frisch, Ilaria Ciofini, Carlo Adamo, Donald G. Truhlar
Summary: Theoretical characterization of reactions of complex molecules requires accurate determination of the relative energies of intermediates and transition states. In this study, the DLPNO-CCSD(T) method was employed to provide benchmark values for Diels-Alder transition states leading to strained pentacyclic adducts. Various wave function and density functional methods were compared for their prediction of absolute and relative barrier heights. The results show that only a few density functionals can satisfactorily predict absolute barrier heights, while relative barrier heights are more accurate. The findings of this study can guide the selection of density functionals for future studies on crowded, strained transition states of large molecules.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Michele Turelli, Ilaria Ciofini, Qinfan Wang, Alistar Ottochian, Frederic Labat, Carlo Adamo
Summary: Organic luminophores with luminescence enhancement in solid state have great potential for the development of functional materials. However, the understanding of the molecular interactions responsible for the macroscopic response is limited. Theoretical frameworks that provide mechanistic explanations and quantitative predictions are important for the understanding of solid-state luminescence enhancement.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Andrew M. Teale, Trygve Helgaker, Andreas Savin, Carlo Adamo, Balint Aradi, Alexei Arbuznikov, Paul W. Ayers, Evert Jan Baerends, Vincenzo Barone, Patrizia Calaminici, Eric Cances, Emily A. Carter, Pratim Kumar Chattaraj, Henry Chermette, Ilaria Ciofini, T. Daniel Crawford, Frank De Proft, John F. Dobson, Claudia Draxl, Thomas Frauenheim, Emmanuel Fromager, Patricio Fuentealba, Laura Gagliardi, Giulia Galli, Jiali Gao, Paul Geerlings, Nikitas Gidopoulos, Peter M. W. Gill, Paola Gori-Giorgi, Andreas Gorling, Tim Gould, Stefan Grimme, Oleg Gritsenko, Hans Jorgen Aagaard Jensen, Erin R. Johnson, Robert O. Jones, Martin Kaupp, Andreas M. Koster, Leeor Kronik, Anna Krylov, Simen Kvaal, Andre Laestadius, Mel Levy, Mathieu Lewin, Shubin Liu, Pierre-Francois Loos, Neepa T. Maitra, Frank Neese, John P. Perdew, Katarzyna Pernal, Pascal Pernot, Piotr Piecuch, Elisa Rebolini, Lucia Reining, Pina Romaniello, Adrienn Ruzsinszky, Dennis R. Salahub, Matthias Scheffler, Peter Schwerdtfeger, Viktor N. Staroverov, Jianwei Sun, Erik Tellgren, David J. Tozer, Samuel B. Trickey, Carsten A. Ullrich, Alberto Vela, Giovanni Vignale, Tomasz A. Wesolowski, Xin Xu, Weitao Yang
Summary: This paper provides an informal review and discussion on the history, present status, and future of density-functional theory (DFT) by 70 workers in the field. The format of a roundtable discussion allowed participants to express their views through 302 individual contributions to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper offers a comprehensive snapshot of DFT in 2022.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Cosimo Micheletti, Qinfan Wang, Francesco Ventura, Michele Turelli, Ilaria Ciofini, Carlo Adamo, Andrea Pucci
Summary: This study explores the preparation of red-emitting luminescent solar concentrators using an aggregation-induced enhanced emission fluorophore and investigates the behavior of the fluorophore in different environments. The results show that by suppressing the aggregation of the fluorophore, the luminescence performance and quantum yield can be improved, leading to enhanced performance of the luminescent solar concentrators.