Article
Green & Sustainable Science & Technology
Thirusangumurugan Senthamarai, Fairoosa Poovan, Asma M. Alenad, Nils Rockstroh, Jabor Rabeah, Stephan Bartling, Eszter Barath, Kishore Natte, Rajenahally Jagadeesh
Summary: The synthesis and functionalization of nitrogen-containing compounds is important for their wide range of applications. This study reports a Cu-catalyzed aerobic oxidation process for the preparation of nitriles and primary amides from alcohols and ammonia. The use of supported copper oxide nanoparticles as catalysts showed good efficiency and selectivity for the synthesis of various nitriles and primary amides.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Physical
Rahul Sharma, Avijit Mondal, Arup Samanta, Dipankar Srimani
Summary: In this study, a single SNS ligand derived nickel complex was used for the selective synthesis of alkylated and alkenylated fluorenes. The protocol demonstrated success with a wide range of substrates, including various substituted fluorenes and aliphatic alcohols with a distal double bond. Furthermore, the synthesis of an antimalarial drug analogue and various post-modifications of alkylated fluorenes were achieved, showcasing the versatile synthetic utility of the method.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Qiao Chu, Zhaoyue Feng, Sumin Zhang, Ping Liu, Peipei Sun
Summary: An electrochemical three-component reaction cascade Mumm rearrangement was developed for the synthesis of imides. Commercially available aryl acids, nitriles, and alkylbenzenes were used as substrates without pre-functionalization, and the reactions were conducted under transition metal- and chemical oxidant-free conditions. Subsequent hydrolysis or reduction of the imide products could be easily achieved to synthesize amides, as well as primary or tertiary amines.
Article
Chemistry, Organic
Guofu Zhang, Huihui Miao, Chenfei Guan, Chengrong Ding
Summary: The direct transformation of aryl carboxylic acids to aryl nitriles has been achieved through palladium-catalyzed decarbonylative cyanation without the use of a base. Successful analysis of the decarbonylative cyanation of drug molecules and gram-scale reactions validates the practicality and operability of this method.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Manuel Freis, Moritz Balkenhohl, David M. Fischer, Tony Georgiev, Roman C. Sarott, Erick M. Carreira
Summary: The cobalt-catalyzed aminocyclization of unsaturated N-acyl sulfonamides in the presence of oxygen was reported, leading to the formation of α- and d-lactam aldehydes. Enantiomerically enriched α- and d-lactam alcohols were obtained by using an optically active cobalt catalyst. The obtained α-lactam aldehydes and alcohols were further elaborated into useful building blocks.
Article
Chemistry, Organic
Manuel Freis, Moritz Balkenhohl, David M. Fischer, Tony Georgiev, Roman C. Sarott, Erick M. Carreira
Summary: This paper reports a cobalt-catalyzed aminocyclization of unsaturated N-acyl sulfonamides in the presence of oxygen, leading to α- and d-lactam aldehydes. Chiral cobalt catalysts were utilized to obtain enantiomerically enriched α- and d-lactam alcohols. The α-lactam aldehydes and alcohols obtained can be elaborated into useful building blocks.
Article
Chemistry, Physical
Hafsa Karroum, Sergey Chenakin, Sergei Alekseev, Viacheslav Iablokov, Yizhi Xiang, Vincent Dubois, Norbert Kruse
Summary: This study presents a one-step-one-pot synthesis of chain-lengthened aliphatic amines and nitriles using potassium-promoted Co/MnOx catalysts, showing that the reaction can be tuned by adjusting the H-2/CO ratio. Additionally, the addition of NH3 strongly favors the formation of chain-lengthened olefins over alkanes.
Article
Chemistry, Organic
Yushi Tan, Ya-Ping Han, Yuecheng Zhang, Hong-Yu Zhang, Jiquan Zhao, Shang-Dong Yang
Summary: A facile and efficient method for the synthesis of primary phosphinamides from Ar2P(O)-H reagents using stable and readily available ammonium carbonate as an ammonia source is disclosed for the first time. This ethyl bromoacetate-mediated primary amination proceeds smoothly under mild and simple conditions, without the need for any metal catalyst or oxidant. Furthermore, this method is suitable for constructing P-N or P-O bonds using a variety of amines, alcohols, and phenols, with features of easy operation, good functional group tolerance, and broad substrate scope.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Yo-hei Nagasaki, Masazumi Tamura, Mizuho Yabushita, Yoshinao Nakagawa, Keiichi Tomishige
Summary: The silica-supported molybdenum oxide catalyst showed high efficiency and reusability in the dehydration of various amides. The results of catalyst characterizations and activity tests revealed that the strong acid sites formed by the interaction between silanol groups and molybdenum oxide species, along with the acid-base pair sites, played a crucial role in the dehydration reaction.
Article
Multidisciplinary Sciences
Wenjun Yang, Ivan Yu Chernyshov, Robin K. A. van Schendel, Manuela Weber, Christian Muller, Georgy A. Filonenko, Evgeny A. Pidko
Summary: In this study, a highly efficient manganese pincer pre-catalyst was reported, displaying high TOF values (up to 41,000 h(-1)) and stability (TON up to 200,000) at loadings as low as 5-200 ppm. The crucial role of catalyst activation step for the catalytic performance and stability of the system was highlighted, with activation using hydride donor promoters significantly improving catalytic performance and eliminating induction times. Manganese-based hydrogenation catalysts are shown to be sensitive to high temperatures, but this pre-catalyst offers a promising alternative.
NATURE COMMUNICATIONS
(2021)
Article
Engineering, Environmental
Talifhani Mushiana, Zhiang Shao, Mustafa Khan, Ning Zhang, Mingming Ma
Summary: The electrocatalytic oxidation of benzyl alcohol and ammonia on NiCo nitride and oxide co-localized on carbon cloth electrode enables selective synthesis of nitriles. The tandem electrocatalyst with two interfaces shows synergistic activity and selectivity superior to single interface catalyst. This study highlights the potential of cascade reactions in designing electrocatalysts.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Jayeeta Bhattacharjee, Parveen Rawal, Suman Das, Adimulam Harinath, Puneet Gupta, Tarun K. Panda
Summary: In this paper, the synthesis of titanium catalysts through salt metathesis reaction is reported, and the detailed steps of a series of reactions are described. The study found that the titanium catalyst exhibited good selective catalytic activity towards ester functionalities under solvent-free conditions, and the key steps of the reaction mechanism were revealed through DFT studies.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Li Liu, Yingdong Zhou, Lixian Guo, Guiying Li, Changwei Hu
Summary: A method for producing nitrogen-containing compounds from natural microalgae was developed and the effects of different conditions on the yield were studied. Addition of ZrO2 resulted in an increase in the yields of fatty amides and nitriles, while the total yield of fatty acids decreased.
Article
Chemistry, Inorganic & Nuclear
Pablo Hermosilla, Pilar Garcia-Orduna, Pablo J. Sanz Miguel, Victor Polo, Miguel A. Casado
Summary: The reaction of an amido pincer complex with carbon dioxide resulted in a neutral complex, which then underwent a coupling reaction with primary amines to form cationic complexes. The study revealed a novel reactivity trend in alkyne activation, showing a metal-ligand cooperative mechanism involving electrophilic attack and proton rearrangement.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Vanessa Vethacke, Vanessa Claus, Martin C. Dietl, Daniel Ehjeij, Arne Meister, Jonas F. Huber, Leon K. Paschai Darian, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Summary: A variety of unsymmetric diaryl gold N-acyclic carbene (NAC) complexes were successfully synthesized by three different methods, allowing access to new complexes and overcoming previous limitations in the isonitrile route. These new complexes also proved to be successful as pre-catalysts in gold-catalyzed phenol synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Viktoriia Zubar, Andreas T. Haedler, Markus Schuette, A. Stephen K. Hashmi, Thomas Schaub
Summary: This report discusses the promising method of utilizing plastic waste through chemical recycling, specifically hydrogenative depolymerization using a Mn pincer complex catalyst. The key to success lies in the combination of the catalyst with elevated temperatures and appropriate solvents to ensure sufficient solubility of the polymers. The process successfully depolymerizes a wide range of polyurethane samples, releasing polyetherols and diaminotoluene in high yields.
Article
Chemistry, Applied
Sina Witzel, Marvin Hoffmann, Matthias Rudolph, Frank Rominger, Andreas Dreuw, A. Stephen K. Hashmi
Summary: The study reports an unprecedented reactivity of mononuclear gold catalysts in a radical chain mechanism, where gold acts as both a classical catalyst and an active partner. Through thorough experimental and theoretical analysis, it was shown that the mechanism is initiated by an aryl radical formed in the presence of blue LEDs and MeOH, leading to the oxidation of gold(I) and subsequent formation of the desired product.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Fabian Stuck, Martin C. Dietl, Maximilian Meissner, Finn Sebastian, Matthias Rudolph, Frank Rominger, Petra Kraemer, A. Stephen. K. Hashmi
Summary: Efficient synthetic approaches for the incorporation of nitrogen into polyaromatic compounds (PACs) in different patterns as stabilising moiety for pi-extended systems and modification tool for optoelectronic properties remain a challenge. The study developed a new versatile pathway to napthyridine-based PACs as non-symmetric and regioisomeric pendant to pyrazine-based PACs. The key steps involve a gold-catalysed synthesis of 2-aminoquinolines and in situ desulfonation, highlighting the influence of attached substituents on the electronic properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Viktoriia Zubar, Niels Lichtenberger, Mathias Schelwies, Thomas Oeser, A. Stephen K. Hashmi, Thomas Schaub
Summary: The hydrogenation of (+)-Sclareolide to (-)-ambradiol catalyzed by a manganese pincer complex was achieved with high yield. The catalyst is easy to prepare, and the reaction conditions are relatively mild, with reproducible experimental results.
Article
Chemistry, Multidisciplinary
Robin Heckershoff, Steffen Maier, Thomas Wurm, Philipp Biegger, Kerstin Broedner, Petra Kraemer, Marvin T. Hoffmann, Lukas Eberle, Jana Stein, Frank Rominger, Matthias Rudolph, Jan Freudenberg, Andreas Dreuw, A. Stephen K. Hashmi, Uwe H. F. Bunz
Summary: The transition-metal-catalyzed cyclization of bissilylethynylated N,N'-dihydrotetraazapentacene (TIPS-TAP-H-2) into bissilylated cyclopenta[fg,qr]pentacenes is reported. Depending on the catalyst, either none, one, or two silyl groups migrate and change their positions in the formed five-membered rings. The optoelectronic properties are similar, while the packing motifs differ greatly. Control experiments and quantum chemical calculations were performed to investigate the reaction mechanism and the selectivity of the silyl shift.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Multidisciplinary Sciences
Hongming Jin, Wen-Yan Tong, Jing Zhang, Matthias Rudolph, Frank Rominger, Xu Shen, Shuanglin Qu, A. Stephen K. Hashmi
Summary: In this study, the divergent reactivity of Pt(II) and Au(III) catalysts in intermolecular annulations was investigated. It was found that the Au(III) catalysts are more likely to produce smaller ring structures. The results of this study are important for understanding the selective reactions of metal carbene intermediates.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Maximilian Menche, Philippe Klein, Marko Hermsen, Robert Konrath, Tamal Ghosh, Jedrzej Wysocki, Martin Ernst, A. Stephen K. Hashmi, Ansgar Schaefer, Peter Comba, Thomas Schaub
Summary: The influence of the ligand backbone on the enantioselectivity in the ruthenium-catalyzed direct asymmetric reductive amination was studied. It was found that using ligands with a larger bite angle could significantly increase the enantioselectivity. However, despite various attempts, increasing the enantioselectivity was not possible with larger ligand backbones.
Article
Chemistry, Multidisciplinary
Robin Heckershoff, Garrett May, Janika Daeumer, Lukas Eberle, Petra Kraemer, Frank Rominger, Matthias Rudolph, Florian F. Mulks, A. Stephen K. Hashmi
Summary: This study discovered an entropy-induced selectivity switch in the gold-catalyzed intramolecular hydroarylation of 2-ethynyl N-aryl indoles, leading to the synthesis of indolo[1,2-a]quinolines. Experimental and computational investigations provided insight into the mechanism of this uncommon selectivity phenomenon. The methodology demonstrated high functional group tolerance and the potential for diverse applications as functional materials.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Alban Falconnet, Jan-Dirk Arndt, A. Stephen K. Hashmi, Thomas Schaub
Summary: The Friedel-Crafts sulfonylation for the synthesis of diaryl sulfones derivatives was achieved using triflic acid as the catalyst. The method showed good to excellent yield and high selectivity, and the catalyst and excess arene could be easily recovered and re-used.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zuo Zuo Wu, Tapas Adak, Martin C. Dietl, Tao Wang, Chao Hu, Hongwei Shi, Petra Kraemer, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Summary: The study presents a novel gold-catalyzed 2-fold reaction of a bromoalkyne with anthranils to produce alpha-ketoamides. This method provides a new synthetic approach for preparing this functional group.
Article
Chemistry, Applied
Philipp M. Stein, Jonas Pascher, Jonas Stracke, Victor S. Levacher, Josefine A. Wagner, Frank Rominger, Thomas Oeser, Matthias Rudolph, A. Stephen K. Hashmi
Summary: This article presents an efficient gold-catalyzed method for the functionalization of 1,3-butadiyne derivatives. The starting materials are synthesized via simple Glaser Coupling and converted into versatile functionalized 1,3-butadiene derivatives under mild conditions using alcohol as a solvent and nucleophile. The method offers an attractive and highly effective approach to versatile functionalized 1,3-butadiene derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Robin Heckershoff, Lukas Eberle, Garrett May, Petra Kraemer, Frank Rominger, Matthias Rudolph, A. Stephen K. Hashmi
Summary: The recently developed gold-catalyzed synthesis of indolo[1,2-a]quinolines has been successfully expanded to bidirectional approaches, allowing access to two heptacyclic structural motifs. New nitrogen-containing heptacycles, benzobispyrrolo[1,2-a]quinolines, were synthesized using alkynylated benzodipyrrole derivatives. The study revealed important structure-effect relationships between solid-state structures and photophysical properties.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Steffen Maier, Robin Heckershoff, Nikolai Hippchen, Kerstin Broedner, Frank Rominger, Jan Freudenberg, A. Stephen K. Hashmi, Uwe H. F. Bunz
Summary: In this study, brominated pentannulated dihydrotetraazapentacenes were synthesized through gold- or palladium-catalyzed cyclization of TIPS-ethynylated dihydrotetraazaacenes, followed by Sonogashira alkynylation and Rosenmund-von Braun cyanation for post-functionalization. Characterization in organic field-effect transistors confirmed these species to act as n-type semiconductors.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Hongwei Shi, Jun Li, Tao Wang, Matthias Rudolph, A. Stephen K. Hashmi
Summary: A catalyst- and additive-free sunlight-induced strategy for the autoxidation of a wide range of aldehydes to carboxylic acids is described. This method utilizes air as the source of oxygen and sunlight as the light source, offering green, highly atom-efficient, and low-cost synthesis. The reaction can be easily scaled up and can proceed smoothly even at lower temperature and in natural light.
