Article
Biochemistry & Molecular Biology
Guillaume Coin, Jean-Marc Latour
Summary: This review discusses the efficient and selective catalytic systems achieved through engineered hemoproteins for introducing N functionalities in organic molecules. The study highlights the importance of the rationale behind enzymatic engineering and compares in vitro and in vivo nitrene transfer processes by cytochromes P450. Mechanistic aspects are emphasized and compared with current molecular knowledge of the reactions, with forthcoming developments outlined.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Physical
Yungen Liu, Ka-Pan Shing, Vanessa Kar-Yan Lo, Chi-Ming Che
Summary: Transition-metal-catalyzed direct C-N bond formation reactions have been widely used for the synthesis of nitrogen-containing compounds. Iron catalysts are promising due to their cost-effectiveness and environmental sustainability, while ruthenium complexes provide more stability for studying the reaction mechanism. This Perspective summarizes the recent developments in iron and ruthenium complexes supported by macrocyclic or polydentate ligands for catalytic amination reactions involving metal imido/nitrene intermediates, and discusses the current limitations and potential opportunities for future research.
Article
Chemistry, Multidisciplinary
Jordan Donat, Patrick Dubourdeaux, Martin Clemancey, Julia Rendon, Clara Gervasoni, Morgan Barbier, Jessica Barilone, Jacques Pecaut, Serge Gambarelli, Pascale Maldivi, Jean-Marc Latour
Summary: This study investigates the mechanism of nitrene generation in nitrene transfer reactions. The researchers found that the same active species was formed, regardless of whether the metal ion was divalent or trivalent. Through a combination of spectroscopic and computational studies, they identified the catalytically active species and revealed its formation mechanism.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Yuan Bin-Bin, Song Jin-Shuai, Yan Xue-Yuan, Xiao Han, Li Chun-Sen
Summary: Density functional theory calculations were used to investigate the mechanism of ring-closing sulfoxide imidation catalyzed by Fe(II)-phthalocyanine. The results revealed a triplet state diradical structure for the iron phthalocyanine nitrene intermediate, and provided insight into the reaction barriers and mechanism.
CHINESE JOURNAL OF STRUCTURAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Erwan Brunard, Vincent Boquet, Elsa Van Elslande, Tanguy Saget, Philippe Dauban
Summary: This study reports a catalytic intermolecular amination of nonactivated tertiary C(sp(3))-H bonds using substrates with an activated benzylic site to achieve high yields of alpha, alpha, alpha-trisubstituted amides. The synergistic combination of a rhodium(II) complex and tert-butylphenol sulfamate results in selective functionalization of the tertiary C(sp(3))-H bond under mild oxidative conditions. The catalytic system is robust, requiring only 0.01 mol % of catalyst for a 50 mmol scale reaction, and the TBPhs group can be easily removed to obtain NH-free amines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Benjamin S. Mitchell, Andrei Chirila, Daniel Y. Zhou, Jonathan A. Kephart, Alexandra Velian
Summary: This study provides insights into how distal changes regulate the affinity for substrates and tune the catalytic activity of Fe/Co/Se clusters. The stereoelectronic requirements of Fe/Co6Se8 clusters for substrate affinity are investigated. The impact of distal changes on substrate affinity, electronic properties, and catalytic activity is explored. The study reveals the dynamic interactions between the substrate, active site, and support, and their role in substrate activation.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Matthew T. Whited, Wenlai Han, Helen J. Jin-Lee, Zach DiNardo, Emma Watson, Jia Zhang, Daniela Kohen
Summary: A cobalt silylene linkage enables metal/ligand cooperative activation and significantly improves the catalytic isocyanate generation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xin Nie, Chen-Xi Ye, Sergei I. Ivlev, Eric Meggers
Summary: A new synthetic method for the preparation of non-racemic 5-membered cyclic carbonates from abundant alcohols has been reported. The conversion of the alcohol into an azanyl carbonate, followed by a chiral-at-ruthenium catalyzed cyclization, resulted in chiral cyclic carbonates with yields of up to 95% and enantiomeric excess (ee) of up to 99%. This method involves a nitrene-mediated intramolecular C(sp(3))-H oxygenation, which includes an unusual 1,7-hydrogen atom transfer within a ruthenium nitrene intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Rabina Pradhan, Kaylaa L. Gutman, Abu Mas Ud, Elliott B. Hulley, Kristopher V. Waynant
Summary: Coordination complexes were synthesized using azothioformamide (ATF) ligands and Cu(I) salts. These complexes were then used as catalysts for the insertion of carbon dioxide into terminal alkynes. Optimal catalytic conditions were achieved using a specific Cu(I) dimer and Cs2CO3 as the base under specific temperature and pressure conditions. The reaction yield ranged from 47% to 99% for various substrates, and a proposed mechanism along with likely intermediates was provided.
Article
Chemistry, Multidisciplinary
Jing-Jing Tang, Xiaoqiang Yu, Yi Wang, Yoshinori Yamamoto, Ming Bao
Summary: A visible-light-driven iron-catalyzed nitrene transfer reaction for intermolecular C-N bond formation is developed, showing high yields and a broad substrate scope under mild conditions. Mechanistic studies suggest a radical pathway, with computational studies revealing the importance of visible-light-induced conversion for the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Tao Lu, Fangfang Zhang, Xiao-Yan Wang, Kexin Wang, Ziyong Li, Jun Yin, Sheng Hua Liu
Summary: The study successfully designed and synthesized four novel dithienylethene-based complexes, which exhibited good photochromic behavior. The research also found a slight effect of alkyl chain length on the photochromic properties.
Article
Chemistry, Multidisciplinary
Zarick Juliana Diaz-Puerto, Alvaro Raya-Baron, Piet W. N. M. van Leeuwen, Juan M. Asensio, Bruno Chaudret
Summary: A new method for determining the surface temperature of magnetically heated nanoparticles in solution was described, utilizing the temperature dependency of the catalytic performances of iron carbide nanoparticles coated with ruthenium. The correlation between nanoparticle surface temperature and magnetic field was established and very high surface temperatures were estimated in different solvents, consistent at a given magnetic field and exceeding some solvent boiling points.
Article
Chemistry, Physical
Guillaume Coin, Patrick Dubourdeaux, Frederic Avenier, Ranjan Patra, Ludovic Castro, Colette Lebrun, Pierre-Alain Bayle, Jacques Pecaut, Genevieve Blondin, Pascale Maldivi, Jean-Marc Latour
Summary: Multicomponent reactions are of great interest in synthetic chemistry for their efficiency improvement, but understanding their mechanisms is crucial for optimization. Integrated experimental and theoretical approaches are powerful tools to study these mechanisms at the molecular level, providing insights into the complexity of the reactions and guiding the development of more efficient synthetic routes.
Article
Chemistry, Multidisciplinary
Xinxin Tang, Hidetoshi Noda, Masakatsu Shibasaki
Summary: The article presents a new design principle for the modification of Rh2(esp)2, which involves ligand modification to freeze the conformational dynamics of the parent catalyst, thus allowing for the isolation of two conformationally distinct complexes. The utility of conformational fixation in the development of stereoselective catalysts for nitrene transfer reactions has been demonstrated in three model cases.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Valentina Ferraro, Roberto Sole, Lucia Alvarez-Miguel
Summary: Three neutral Cu(I) complexes with different triatomic pseudohalogen ligands (SCN-, OCN-, and N-3(-)) and 2,6-dimethylphenyl isocyanide (CNXyl) were successfully synthesized and characterized. The solid-state structures were determined through single-crystal X-ray diffraction, revealing unexpected bridging coordination modes in the case of OCN- and N-3(-). All the complexes showed interesting catalytic activity in azide-alkyne cycloaddition reactions, particularly the cyanato and azido Cu(I) complexes, which yielded 1,4-disubstituted-1,2,3-triazoles with high yields and 0.5 mol% of catalyst at 50 & DEG;C for 24 h. The azido Cu(I) complex also induced intramolecular CuAAC reactions in the presence of dimethyl acetylenedicarboxylate and benzyl bromide/phenylacetylene.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Matthew R. Golder, Lev N. Zakharov, Ramesh Jasti
PURE AND APPLIED CHEMISTRY
(2017)
Article
Chemistry, Multidisciplinary
Matthew R. Golder, Yivan Jiang, Paul E. Teichen, Hung V. T. Nguyen, Wencong Wang, Nicole Milos, Seth A. Freedman, Adam P. Willard, Jeremiah A. Johnson
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Engineering, Biomedical
Matthew R. Golder, Jenny Liu, Jannik N. Andersen, Michail V. Shipitsin, Farrukh Vohidov, Hung V. -T. Nguyen, Deborah C. Ehrlich, Sung Jin Huh, Bhavatarini Vangamudi, Kyriakos D. Economides, Allison M. Neenan, James C. Ackley, Joelle Baddour, Sattanathan Paramasivan, Samantha W. Brady, Eric J. Held, Lawrence A. Reiter, Jennifer K. Saucier-Sawyer, Paul W. Kopesky, Donald E. Chickering, Peter Blume-Jensen, Jeremiah A. Johnson
NATURE BIOMEDICAL ENGINEERING
(2018)
Correction
Engineering, Biomedical
Matthew R. Golder, Jenny Liu, Jannik N. Andersen, Michail V. Shipitsin, Farrukh Vohidov, Hung V. -T. Nguyen, Deborah C. Ehrlich, Sung Jin Huh, Bhavatarini Vangamudi, Kyriakos D. Economides, Allison M. Neenan, James C. Ackley, Joelle Baddour, Sattanathan Paramasivan, Samantha W. Brady, Eric J. Held, Lawrence A. Reiter, Jennifer K. Saucier-Sawyer, Paul W. Kopesky, Donald E. Chickering, Peter Blume-Jensen, Jeremiah A. Johnson
NATURE BIOMEDICAL ENGINEERING
(2018)
Article
Chemistry, Multidisciplinary
Hung V. -T. Nguyen, Alexandre Detappe, Nolan M. Gallagher, Hui Zhang, Peter Harvey, Changcun Yan, Clelia Mathieu, Matthew R. Golder, Yivan Jiang, Maria Francesca Ottaviani, Alan Jasanoff, Andrzej Rajca, Irene Ghobrial, P. Peter Ghoroghchian, Jeremiah A. Johnson
Article
Polymer Science
Matthew R. Golder, Hung V. -T. Nguyen, Nathan J. Oldenhuis, Julian Grundler, Ellane J. Park, Jeremiah A. Johnson
Editorial Material
Chemistry, Multidisciplinary
Laura K. G. Ackerman-Biegasiewicz, Daniela M. Arias-Rotondo, Kyle F. Biegasiewicz, Elizabeth Elacqua, Matthew R. Golder, Laure V. Kayser, Jessica R. Lamb, Christine M. Le, Nathan A. Romero, Sidney M. Wilkerson-Hill, Dwight A. Williams
ACS CENTRAL SCIENCE
(2020)
Article
Chemistry, Multidisciplinary
Teng-Wei Wang, Pin-Ruei Huang, Jayme L. Chow, Werner Kaminsky, Matthew R. Golder
Summary: The study introduces a novel ring-expansion metathesis polymerization initiator CB6, which improves the synthesis kinetics and initiator stability of cyclic macromolecules through careful design features and ligand modifications, serving as an adaptable platform for the research and application of cyclic macromolecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Ruth L. Maust, Penghao Li, Baihao Shao, Sarah M. Zeitler, Peiguan B. Sun, Harrison W. Reid, Lev N. Zakharov, Matthew R. Golder, Ramesh Jasti
Summary: This study demonstrates the design and synthesis of controllable carbon nanohoop polymers with tunable fluorescence emission and supramolecular responses, achieved through a combination of organic synthesis and polymer synthesis methods.
ACS CENTRAL SCIENCE
(2021)
Article
Chemistry, Organic
Christine M. Morrison, Matthew R. Golder
Article
Chemistry, Multidisciplinary
Progyateg Chakma, Sarah M. M. Zeitler, Fabio Baum, Jiatong Yu, Waseem Shindy, Lilo D. D. Pozzo, Matthew R. R. Golder
Summary: This study presents an energy-conscious controlled radical polymerization method by combining mechanochemistry and electron-transfer processes. A mechanoredox reversible addition-fragmentation chain transfer (RAFT) polymerization process using piezoelectric barium titanate and a diaryliodonium initiator with minimal solvent usage is demonstrated. It offers exquisite control over the dispersity and chain length of poly(meth)acrylate, presenting an alternative approach to the synthesis of semifluorinated polymers without exotic solvents and reagents. This chemistry holds great importance for the sustainable development of materials in energy, biomedical, and engineering fields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mercie N. Hodges, Matthew J. Elardo, Jinyoung Seo, Alexander F. Dohoda, Forrest E. Michael, Matthew R. Golder
Summary: The accumulation of end-of-life plastics poses ongoing environmental concerns. In this study, a method is proposed to upcycle polybutadiene, a commonly used commercial rubber, through a mild, metal-free allylic amination reaction. The resulting materials exhibit tunable thermal and surface wetting properties. Importantly, this approach maintains the original alkene microstructure without any evidence of olefin reduction, olefin transposition, and/or chain scission. The findings suggest potential applications in the remediation of complex elastomers and vulcanized rubbers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Adelaide M. Levenson, Christine M. Morrison, Pin-Ruei Huang, Teng-Wei Wang, Zak Carter-Schwendler, Matthew R. Golder
Summary: The synthesis of well-defined cyclic polymers is crucial for various applications. This study demonstrates a method to synthesize controlled and low-dispersity cyclic poly(norbornene) by adding pyridine to the tethered ruthenium-benzylidene REMP initiator.
Article
Chemistry, Multidisciplinary
Sarah M. Zeitler, Progyateg Chakma, Matthew R. Golder
Summary: Mechanically-induced redox processes offer a promising alternative to conventional thermal and photochemical synthetic methods and provide exquisite control over the synthesis of high molecular weight polymers.
Review
Polymer Science
Teng-Wei Wang, Matthew R. Golder
Summary: The exploration of macromolecular topology provides common ground amongst chemists, material scientists, mathematicians, and artists. Different polymer architectures have unique physical properties and their topological-dependent properties are a fusion of symmetry and polymer physics. Specifically, cyclic macromolecules have distinct characteristics compared to their linear counterparts due to the lack of chain ends.