Article
Chemistry, Organic
Jun Li, Yong Yuan, Xiazhen Bao, Tongzhi Sang, Jie Yang, Congde Huo
Summary: An intermolecular vicinal O-N difunctionalization reaction of olefins with oxime esters has been developed using energy transfer catalysis.
Article
Chemistry, Organic
Lu-Wen Zhang, Xiao-Jun Deng, Dong-Xu Zhang, Qin-Qin Tian, Wei He
Summary: This study introduces a novel method for the synthesis of amino lactones and explores the influence of the iodoarene precatalyst structure on reaction rate, demonstrating its selective adjustment effect in aminolactonization and oxylactonization. Furthermore, the feasibility of asymmetric aminolactonization catalyzed by a chiral iodoarene precatalyst was verified through preliminary experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Finn Burg, Tomislav Rovis
Summary: A method for the internal and highly diastereoselective amino oxygenation of 1,3-dienes has been developed, catalyzed by a cationic heptamethylindenyl (Ind*) Rh(III) complex, filling the gap in the selective amino oxygenation of 1,3-dienes at the internal position.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Georgina Kirby, Guillaume Prestat, Farouk Berhal
Summary: Herein, an atom-economical intermolecular iron-catalyzed oxyamination of alkenes is reported. The insertion of oxygenated and nitrogenated moieties from the hydroxylamine substrate was observed with full regio- and chemo-selectivity for terminal alkenes in good yields. HFIP solvent appeared to synergistically promote the formation of the oxyaminated products with the iron catalyst. Preliminary mechanistic studies suggest a pathway involving aziridination followed by in situ ring opening.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ya-Li Wu, Min Jiang, Li Rao, Ying Cheng, Wen-Jing Xiao, Jia-Rong Chen
Summary: A three-component 1,2-aminooxygenation reaction of 1,3-dienes by dual photoredox and copper catalysis is described. This reaction utilizes N-aminopyridinium salts as N-centered radical precursors and nucleophilic alcohols as oxygen sources, providing modular and practical access to 1,2-aminoalkoxylation products with high yields and regioselectivity.
Article
Chemistry, Multidisciplinary
Yaxin Zeng, Ying Xia
Summary: The direct synthesis of gem-difluorinated carbocyclic molecules has long been a challenge in organic chemistry. Here, a Rh-catalyzed [3+2] cycloaddition reaction between gem-difluorinated cyclopropanes and internal olefins has been developed, providing an efficient method to synthesize gem-difluorinated cyclopentanes with good functional group compatibility, excellent regioselectivity, and good diastereoselectivity. The resulting products can also be further transformed into various mono-fluorinated cyclopentenes and cyclopentanes, demonstrating the potential of this reaction as a strategy for synthesizing other gem-difluorinated carbocyclic molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Vladimir I. Kurganskiy, Roman Ottenbacher, Mikhail Shashkov, Evgenii P. Talsi, Denis G. Samsonenko, Konstantin P. Bryliakov
Summary: In this paper, the direct selective C-H lactonization of fatty acids (C5-C16) catalyzed by manganese(II) complexes bearing bis-amino-bis-pyridine ligands was reported. The catalyst system used environmentally benign hydrogen peroxide as an oxidant and showed high efficiency, providing gamma-lactones in 60-90% yields under optimized conditions. Remarkably, by changing the reaction conditions, the oxidation of hexanoic acid could be diverted to the formation of delta-caprolactone in up to 67% yield. Furthermore, the possibility of obtaining (omega-1)-hydroxy derivatives from linear C7-C10 acids in up to 48% yields was demonstrated.
Article
Chemistry, Multidisciplinary
Maorui Wang, Chengqian Zhang, Chenggang Ci, Huanfeng Jiang, Pierre. H. Dixneuf, Min Zhang
Summary: Despite the challenges, we have successfully developed a room temperature approach for the direct construction of alpha-hydroxyalkyl cyclic amines through the strategy of electroreductive alpha-hydroxyalkylation. This method offers a broad substrate scope, simplicity in operation, high chemoselectivity, and does not require pressurized H2 gas or transition metal catalysts. The activation of reactants by the zinc ion generated from anode oxidation plays a crucial role in this transformation. This strategy, combined with substrate activation by Lewis acids, is expected to lead to the development of more useful transformations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yanan Wang, Yanyang Bao, Meifang Tang, Zhegao Ye, Zheliang Yuan, Gangguo Zhu
Summary: This review summarises the recent applications of pyridinium salts in the radical-mediated difunctionalization of alkenes. The distinguished properties of pyridinium salts in radical transformations are discussed, and the review is divided into three parts based on the role of pyridinium salts in difunctionalization of alkenes.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hao Wang, Hoimin Jung, Fangfang Song, Shiyang Zhu, Ziqian Bai, Danye Chen, Gang He, Sukbok Chang, Gong Chen
Summary: N-N linkages are important in natural compounds, and a nitrene-mediated intermolecular N-N coupling reaction using iridium or iron catalysis provides a simple and efficient method to synthesize various hydrazides from readily available carboxylic acid and amine precursors. Mechanistic studies show that the nitrogen atom of Ir acyl nitrene intermediates serves as a strong electrophile and can form N-N bonds with high efficiency and chemoselectivity with the assistance of Cl···HN hydrogen bonding.
Article
Chemistry, Physical
Tasiana Reza, Marina A. Tokareva, Natalie K. Dobson, Alexandra L. Shanahan, Kyle Sheather, Christopher Richardson, Sinead T. Keaveney
Summary: The Rh(I)-catalyzed denitrogenative annulation reactions of 1,2,3-thiadiazoles provide a new approach for synthesizing densely functionalized heterocycles. This study investigates the effects of terminal alkyne substituents on regioselectivity, revealing the influence of electronic and steric properties. The findings contribute to the development of a predictive framework for the reaction's regioselectivity.
Article
Chemistry, Organic
Juan Ye, Yang Wang
Summary: A comprehensive study on the mechanisms and origins of the chemoselectivity and regioselectivity of phosphine-catalyzed Rauhut-Currier reaction is performed by DFT. The computational results reveal that the cross R-C reaction is energetically favorable, with head-to-tail product being generated preferentially. The C-C bond formation process is identified as the determining step for regioselectivity and chemoselectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zenghui Ye, Rongjin Zhu, Feng Wang, Haobin Jiang, Fengzhi Zhang
Summary: Atom- and step-economic oxo-azidation and oxo-hydroxyphthalimidation of styrenes were developed under mild electrolytic conditions, leading to efficient synthesis of valuable alpha-azido or hydroxyphthalimide aromatic ketones from readily available starting materials. Mechanism studies revealed two different pathways involved in these transformations.
Article
Chemistry, Multidisciplinary
Pengfei Qian, Shilei Zhang, Fan Luo, Jiarui Wang, Xinyu Zhang, Xuejun Liu, Xiaodong Chen, Wei Wang, Xiaobei Chen
Summary: A co-catalyzed hydrogen-deuterium exchange method has been developed to selectively introduce deuterium at a specific position of enals. The protocol is mild and simple, allowing for high level deuterium incorporation in structurally diverse aromatic-derived enals and dienals.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Takahiro Watanabe, Kyohei Oga, Hiroaki Matoba, Masanori Nagatomo, Masayuki Inoue
Summary: In this study, we report a concise synthesis of Taxol. By designing the carbon and oxygen rings and utilizing radical reactions and catalytic cyclization, we successfully achieved the total synthesis of Taxol. This provides valuable information for designing and executing syntheses of other oxygenated terpenoids with high density.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Sibylle Friess, Anna Benyak, Alberto Herrera, Ana M. Escalona, Frank W. Heinemann, Jens Langer, Dominik Fehn, Daniel Pividori, Alexander Grasruck, Dominik Munz, Karsten Meyer, Romano Dorta
Summary: The oxidative addition of bromine or iodine to an Ir(I) sulfoxide pincer complex leads to the formation of Ir(IV) tris-bromido or tris-iodido complexes, respectively. The reductive elimination of iodine from the Ir(IV)-iodido complex can be achieved without any traps by coordinating ligands or donor solvents. The addition of I- results in the quick generation of an isostructural tris-iodo Ir(III)-ate complex, which can be easily reoxidized back to the Ir(IV)-iodido complex.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Alejandro Cadranel, Lisa Gravogl, Dominik Munz, Karsten Meyer
Summary: This study reports high-valent iron complexes supported by N-heterocyclic carbene (NHC)-anchored, bis-phenolate pincer ligands that undergo ligand-to-metal charge transfer (LMCT) upon photoexcitation. The excited states exhibit a ligand-based, mixed-valence system and intense intervalence charge transfer bands in the near-infrared region. The observations provide insight into the excited-state decay mechanism in high-valent NHC complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Annette Gruenwald, Bhupendra Goswami, Kevin Breitwieser, Bernd Morgenstern, Marti Gimferrer, Frank W. Heinemann, Dajana M. Momper, Christopher W. M. Kay, Dominik Munz
Summary: This study reports three palladium terminal imido complexes with singlet ground states. UV-vis-NIR electronic spectroscopy, high-level computations, and reactivity studies suggest significant palladium(0) singlet-nitrene character. Although the aliphatic nitrene complexes cannot be isolated in pure form, the aryl congener can be characterized by various techniques. The ambiphilic nature of these complexes allows them to catalyze various reactions at or below room temperature.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Kevin Breitwieser, Hilke Bahmann, Robert Weiss, Dominik Munz
Summary: Stabilizing free radicals using C-donor ligands has been investigated by analyzing the pi-donation and pi-acceptance effects. This study provides a new understanding of NHC chemistry and allows for predicting the thermodynamic stability of covalent radicals and quantifying redox non-innocence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Weiqing Mao, Dominik Fehn, Frank W. Heinemann, Andreas Scheurer, Maurice van Gastel, Sergio A. Jannuzzi, Serena DeBeer, Dominik Munz, Karsten Meyer
Summary: This study synthesized a series of cobalt complexes through oxidation reactions of the reactants, and characterized and analyzed them using experimental methods and computational methods, revealing their structures and reaction mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Martin Keilwerth, Weiqing Mao, Sergio A. V. Jannuzzi, Liam Grunwald, Frank W. Heinemann, Andreas Scheurer, Joerg Sutter, Serena DeBeer, Dominik Munz, Karsten Meyer
Summary: Terminal imido complexes of iron have been widely studied in metal-catalyzed nitrogen-transfer chemistry. In this study, a new tris-NHC chelating ligand (TIMMNMes) was used to synthesize and compare two series of iron alkyl imido complexes, including a reactive Fe(V) adamantyl imido intermediate. The stability and reactivity of these complexes were investigated using various characterization techniques and quantum chemical calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ying Kai Loh, Mohand Melaimi, Dominik Munz, Guy Bertrand
Summary: Carbenes, once considered laboratory curiosities, now serve as powerful tools in chemistry and material sciences. This article describes the synthesis of a carbon-based dual ambiphilic carbene, which can activate organic molecules in 1,1- and 1,3-fashion. It also exhibits an unprecedented reversible intramolecular dearomative [3+2] cycloaddition, allowing it to mask itself as an air-stable cycloadduct.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jan Lorkowski, Dylan Bouetard, Patrick Yorkgitis, Milan Gembicky, Thierry Roisnel, Nicolas Vanthuyne, Dominik Munz, Ludovic Favereau, Guy Bertrand, Marc Mauduit, Rodolphe Jazzar
Summary: Organic circularly polarized luminescence (CPL)-active molecular emitters with dynamic propeller-like luminophores were synthesized from cyclic (alkyl) (amino) carbenes (CAACs) in a one-step procedure. These molecules exhibit arene-arene & pi;-delocalization through space and rapid intramolecular inter-system crossing (ISC) in accordance with their helical character.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Cuijuan Zhang, Fabian Dankert, Ziang Jiang, Baolu Wang, Dominik Munz, Jiaxiang Chu
Summary: This study reports the reactions between a neutral Al-I complex and various isocyanides, revealing the step-by-step coupling mechanism through low-temperature NMR monitoring, isotopic labeling, and quantum chemical calculations. Carbene intermediates were confirmed in the reaction with a sterically hindered isocyanide, while a trimerization product and a corresponding carbene intermediate were observed in the reaction with adamantyl isocyanide. Moreover, pentamerization products and the formation of quinoline or indole heterocycles were observed in reactions with sterically less congested isocyanides. Overall, this study provides evidence for the existence of carbene intermediates in FT-type chemistry of aluminium(I) and isocyanides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Weiqing Mao, Zihan Zhang, Dominik Fehn, Sergio A. V. Jannuzzi, Frank W. Heinemann, Andreas Scheurer, Maurice van Gastel, Serena DeBeer, Dominik Munz, Karsten Meyer
Summary: This study describes the synthesis, characterization, and reactivity of a series of cobalt terminal imido complexes supported by an N-anchored tripodal tris(carbene) chelate. The complexes were fully characterized using various spectroscopic and crystallographic techniques. Quantum chemical calculations provided insight into the electronic structures of the compounds. The findings highlight the reactivity of these cobalt imido complexes, including their ability to undergo intramolecular C-H bond amination and nucleophilic addition reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Nicola Marigo, Bernd Morgenstern, Andrea Biffis, Dominik Munz
Summary: Palladium complexes with a novel cyclic (alkyl)(amino)carbene (CAAC) ligand are efficient cross-coupling precatalysts for the Buchwald-Hartwig amination reaction with aryl chlorides. We found that the reduced form of the complexes disproportionates to form a complex and palladium nanoparticles, but still exhibit excellent catalytic activity. In the presence of dioxygen, the CAAC complexes catalyze the formation of diazenes from anilines.
Article
Chemistry, Multidisciplinary
Soosan Hosseinmardi, Andreas Scheurer, Frank W. Heinemann, Nicola Marigo, Dominik Munz, Karsten Meyer
Summary: This study reports a two-step protonation reaction from a Ni-0 precursor to dihydrogen, with the formation of a rare nickel dihydrogen complex in the second protonation step.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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, Multidisciplinary
Sascha Reith, Serhiy Demeshko, Beatrice Battistella, Alexander Reckziegel, Christian Schneider, Andreas Stoy, Crispin Lichtenberg, Franc Meyer, Dominik Munz, C. Gunnar Werncke
Summary: Imidyl and nitrene metal species are important in chemical reactions such as N-functionalisation and aziridination. This article reports on the synthesis and properties of trigonal imido iron complexes, which exhibit different characteristics in their reduced and oxidized forms. Reactivity studies show the ability of these complexes to interact with C-H bonds and other molecules.
Article
Chemistry, Multidisciplinary
Benjamin Wittwer, Nicole Dickmann, Stephan Berg, Daniel Leitner, Lorenzo Tesi, David Hunger, Raphael Gratzl, Joris van Slageren, Nicolas Neuman, Dominik Munz, Stephan Hohloch
Summary: This study elucidates the electronic structure of a rare manganese complex formed by the reaction between a carbazole-based mesoionic carbene ligand and manganese(ii) iodide using a combination of chemical, spectroscopic, magnetic, and computational techniques.
CHEMICAL COMMUNICATIONS
(2022)
