Article
Chemistry, Multidisciplinary
Srimanta Manna, Wei-Jun Kong, Jan-E Backvall
Summary: This study presents an iron(II)-catalyzed biomimetic oxidation of N-heterocycles under aerobic conditions, inspired by oxidations in the respiratory chain. The method utilizes environmentally friendly and inexpensive catalysts, delivering important heterocycles in good-to-excellent yields with a broad substrate scope.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Arnar Guomundsson, Srimanta Manna, Jan-E. Backvall
Summary: This study reports the first Fe-II-catalyzed aerobic biomimetic oxidation of amines, which involves multiple electron transfer steps and is inspired by biological oxidation in the respiratory chain. The use of two coupled catalytic redox systems helps lower the energy barrier and improve the selectivity of the oxidation reaction. Various primary and secondary amines were successfully oxidized in air to their corresponding aldimines or ketimines in good to excellent yield.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Alexios G. Stamoulis, David L. Bruns, Shannon S. Stahl
Summary: This Perspective analyzes the thermodynamic principles underlying catalytic aerobic oxidation reactions and borrows concepts from the study of the oxygen reduction reaction (ORR) in fuel cells. The central role of catalyst overpotential in guiding the development of aerobic oxidation reactions is highlighted. Applications and implications of these concepts are discussed through case studies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yaqing Ye, Yuanyuan Yue, Xiaohui Guo, Junli Chao, Yan Yang, Chunying Sun, Qingzhang Lv, Jianming Liu
Summary: The copper-catalyzed aerobic oxidation enables the selective and efficient transformation of N-pyridylindole for the construction of 11H-pyrido[2,1-b]quinazolin-11-ones. The mechanism involves single-electron-transfer oxidation of N-pyridylindole, capture of molecular oxygen, and extrusion of carbon monoxide to deliver the desired products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Jie Liu, Arnar Guomundsson, Jan-E. Backvall
Summary: This Minireview summarizes recent advances in homogenous aerobic oxidative reactions assisted by electron transfer mediators, emphasizing the cooperative catalytic process and the use of coupled catalyst systems to increase efficiency. The review also highlights progress in photochemical and electrochemical oxidative functionalization, showcasing the mechanisms of these transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Adam Pokluda, Zubair Anwar, Veronika Boguschova, Iwona Anusiewicz, Piotr Skurski, Marek Sikorski, Radek Cibulka
Summary: The study identified a superior photooxidation catalyst with high oxidation power and stability, suitable for oxidation reactions of various substrates, providing potential application prospects for further research.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Alexandra M. Zima, Oleg Y. Lyakin, Anna A. Bryliakova, Dmitrii E. Babushkin, Konstantin P. Bryliakov, Evgenii P. Talsi
Summary: Catalytic approaches to late-stage creation of new C-O bonds, especially via oxygenation of particular C-H groups in complex organic molecules, provide challenging tools for the synthesis of biologically active compounds and candidate drugs. The key role of the oxygen-transferring high-valent iron-oxygen species in selective oxygenation is now well established. In this Personal Account, recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp(3))-H groups are analyzed, with a focus on the factors governing the oxidation chemo- and stereoselectivity.
Article
Chemistry, Physical
Emmanuel D. Silva, Otavio A. L. Alves, Rogerio T. Ribeiro, Rafael C. R. Chagas, Jose A. F. P. Villar, Jefferson L. Princival
Summary: A new base-and halogen-free homogeneous oxidation system was developed in this study, aiming to selectively oxidize allyl, furyl, aryl, and heteroaryl primary alcohols. The system uses CuCl2/TMEDA/TEMPO with mild reaction conditions to produce aldehydes in high yields, and TMEDA as a ligand significantly affects the redox potential in the system.
APPLIED CATALYSIS A-GENERAL
(2021)
Review
Chemistry, Multidisciplinary
Simon Stenkvist, Sara Bacaicoa, Ellymay Goossens, Henrik Sunden
Summary: The use of oxidative N-heterocyclic carbene (NHC) catalysis has gained significant interest due to the ease of transforming simple starting materials into highly functionalized products. However, the use of stoichiometric amounts of high molecular weight oxidants usually generates equivalent amounts of waste. To address this issue, the use of oxygen as the terminal oxidant in NHC catalysis has been developed. This review covers the development of aerobic oxidative carbene catalysis, including NHC-catalyzed reactions with oxygen, strategies for oxygen activation, and selectivity issues under aerobic conditions.
Article
Chemistry, Applied
Adam Pokluda, Zubair Anwar, Veronika Boguschova, Iwona Anusiewicz, Piotr Skurski, Marek Sikorski, Radek Cibulka
Summary: The study demonstrates that the ethylene-bridged 7,8-dimethoxyflavinium salt can effectively carry out photooxidation reactions, even with substrates of high oxidation potential. This salt is characterized by relatively long-lived excited state and high photostability.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Zhitong Zheng, Xu Ma, Xinpeng Cheng, Ke Zhao, Kaylaa Gutman, Tianyou Li, Liming Zhang
Summary: Homogeneous gold catalysis has seen significant development since the turn of the millennium, with oxidative gold catalysis being a vibrant subfield delivering valuable synthetic methods. This comprehensive review covers the mechanistic aspects, oxidants, and synthetic applications of oxidative gold catalysis.
Article
Chemistry, Organic
Anne Renault, Lionel Joucla, Emmanuel Lacote
Summary: In this study, a catalytic formation of 2-tetrazenes was reported, which involved the copper (ii) promoted oxidation of hydrazines in the presence of bipyridine ligands using air or dioxygen as the terminal oxidant. The method successfully produced symmetrical tetrazenes, which were previously prepared using toxic or stoichiometric oxidants. Additionally, the catalytic reaction could be used for the formation of cyclic tetrazenes and dissymmetric structures under certain conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zhenhua Zhang, Julius B. Stueckrath, Stefan Grimme, Andreas Gansaeuer
Summary: Cp2Ti(TFA) is a versatile catalyst for the [2+2] cycloaddition of bisenones through inner-sphere electron transfer, with a unique 5-exo step as the rate-determining step followed by a favorable 4-exo cyclization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Qi Zhao, Yongtao Wang, Yu Wang, Qixuan Hu, Jia Yao, Zeyu Wen, Haoran Li
Summary: The main product from keto acid to alpha-hydroxyl ketone can be effectively controlled by reducing the concentration of FeCl3 catalyst and using DMSO as the solvent. Mechanistic investigations indicate that the same FeCl3-coordinated peroxide intermediate plays a role in both hydroxylation and C-C cleavage routes, and emphasize the role of DMSO as both ligand and reductant. This work provides a new approach for selective aerobic oxidation under Lewis acid catalysis.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Yongzhao Su, Zhicheng Chen, Jiangnan Huang, Hongjuan Wang, Hao Yu, Qiao Zhang, Yonghai Cao, Feng Peng
Summary: Co@C/CNTs catalysts were synthesized and showed high catalytic performance in the oxidation of ethylbenzene. The synergistic effect between Co@C and CNTs played a vital role in enhancing the overall activity of the catalyst.
Article
Chemistry, Multidisciplinary
Man-Bo Li, Jie Yang, Ying Yang, Guo-Yong Xu, Gen Luo, Jianping Yang, Jan-E. Backvall
Summary: A solid amino-supported palladium catalyst is used for the diastereoselective construction of alkyne-substituted cyclopentenol compounds in an oxidative domino reaction. This heterogeneous catalyst shows high efficiency, excellent chemoselectivity, and good recyclability, with the chemoselectivity of the domino reactions easily controlled by switching the solvent and catalyst. Asymmetric syntheses and an oxidative carbocyclization-borylation reaction have also been developed based on this heterogeneous palladium catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Jie Liu, Arnar Guomundsson, Jan-E. Backvall
Summary: This Minireview summarizes recent advances in homogenous aerobic oxidative reactions assisted by electron transfer mediators, emphasizing the cooperative catalytic process and the use of coupled catalyst systems to increase efficiency. The review also highlights progress in photochemical and electrochemical oxidative functionalization, showcasing the mechanisms of these transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Daniels Posevins, Aitor Bermejo-Lopez, Jan-E. Backvall
Summary: An iron-catalyzed cross-coupling reaction of propargyl ethers with Grignard reagents was disclosed, allowing for efficient chirality transfer and preparation of various fluoroalkyl allenes. Additionally, an iron-catalyzed cross-coupling of Grignard reagents with alpha-alkynyl oxetanes and tetrahydrofurans was demonstrated as a straightforward approach towards fully substituted beta- or gamma-allenols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Srimanta Manna, Wei-Jun Kong, Jan-E Backvall
Summary: This study presents an iron(II)-catalyzed biomimetic oxidation of N-heterocycles under aerobic conditions, inspired by oxidations in the respiratory chain. The method utilizes environmentally friendly and inexpensive catalysts, delivering important heterocycles in good-to-excellent yields with a broad substrate scope.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Simon Hilker, Daniels Posevins, C. Rikard Unelius, Jan-E Backvall
Summary: The study presents a straightforward protocol for the chemoenzymatic Dynamic Kinetic Asymmetric Transformation (DYKAT) of alpha-substituted beta-hydroxketones (beta-HKs), resulting in highly enantiomerically enriched products with yields up to 95% and good diastereomeric ratios. The method employs Candida antartica lipase B (CALB) as transesterification catalyst and a ruthenium complex as epimerization catalyst.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Zhiyao Zheng, Luca Deiana, Daniels Posevins, Abdolrahim A. Rafi, Kaiheng Zhang, Magnus J. Johansson, Cheuk-Wai Tai, Armando Cordova, Jan-E Backvall
Summary: In this study, an efficient nanocopper-catalyzed Alder-ene reaction of allenynamides is described. Copper nanoparticles were immobilized on amino-functionalized micro-crystalline cellulose. The reaction exhibited solvent-controlled chemoselectivity, leading to the synthesis of pyrrolines and pyrroles. The heterogeneous copper catalyst showed high efficiency and recyclability in the Alder-ene reaction, making it a highly attractive catalytic system from an economic and environmental perspective.
Article
Chemistry, Inorganic & Nuclear
Daniels Posevins, Jan-E. Backvall
Summary: This minireview discusses the recent advances in iron-catalyzed cross-coupling chemistry, with a focus on the use of propargylic substrates and Grignard reagents as coupling partners.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Correction
Chemistry, Physical
Ning Yuan, Arnar Gudmundsson, Karl P. J. Gustafson, Michael Oschmann, Cheuk-Wai Tai, Ingmar Persson, Xiaodong Zou, Oscar Verho, Eprimeva G. Bajnoczi, Jan-E. Backvall
Article
Chemistry, Multidisciplinary
Jianwei Zhang, Biswanath Das, Oscar Verho, Jan-E Backvall
Summary: Here we describe an electrochemical oxidative palladium-catalyzed carbonylation-carbocyclization reaction for the synthesis of gamma-lactones and spirolactones, exhibiting excellent chemoselectivity. Interestingly, electrocatalysis was found to enhance the reaction rate of the tandem process, leading to a more efficient reaction compared to chemical redox conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Aitor Bermejo-Lopez, Wei-Jun Kong, Pedro J. Tortajada, Daniels Posevins, Belen Martin-Matute, Jan-E Backvall
Summary: A novel iron-catalyzed borylation reaction of propargylic acetates leading to allenylboronates has been developed. This method allows the preparation of di-, tri-, and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-S(N)2' displacement of acetate by boron occurs, allowing chirality transfer to yield enantiomerically enriched allenylboronates.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Luca Deiana, Abdolrahim A. Rafi, Cheuk-Wai Tai, Jan-E. Backvall, Armando Cordova
Summary: We disclose a novel and sustainable tandem-catalysis system for asymmetric synthesis, which is fabricated via bio-inspired self-assembly of artificial arthropod exoskeletons or artificial fungi cell walls containing enzyme and metal nanoparticles. The heterogeneous integrated enzyme/metal nanoparticle system co-catalyzes the dynamic kinetic resolution of primary amines, resulting in high yields and excellent enantiomeric excess of the corresponding amides. The use of natural-based and biocompatible structural components makes the system fully biodegradable and renewable, fulfilling important green chemistry requirements.
Article
Chemistry, Multidisciplinary
Haibo Wu, Zhiyao Zheng, Kaiheng Zhang, Johan Kajanus, Magnus J. Johansson, Armando Cordova, Jan-E. Baeckvall
Summary: A sustainable methodology for the synthesis of chiral allenes was reported using a simple and cheap cellulose supported heterogeneous nanocopper catalyst. High yields and excellent enantiospecificity were achieved for diverse 1,3-di and tri-substituted allenes, and the recycling of the catalyst was also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Luca Deiana, Elham Badali, Abdolrahim A. Rafi, Cheuk-Wai Tai, Jan-E Backvall, Armando Cordova
Summary: This article describes efficient nanogold-catalyzed cycloisomerization reactions of alkynoic acids and allenynamides, resulting in the formation of enol lactones and dihydropyrroles, respectively. The gold nanoparticles were immobilized on thiol-functionalized microcrystalline cellulose and exhibited robust catalytic activity for multiple cycles.
Article
Chemistry, Multidisciplinary
Luca Deiana, Abdolrahim A. Rafi, Jan-E. Baeckvall, Armando Cordova
Summary: Subtilisin integrated artificial plant-cell walls (APCWs) were fabricated by self-assembly with cellulose or nanocellulose as the main component. The resulting APCW catalysts showed excellent catalytic performance for the asymmetric synthesis of (S)-amides. The APCW catalysts could be recycled for multiple cycles without loss of enantioselectivity. The assembled APCW catalysts also cooperated with homogeneous organoruthenium complexes to achieve co-catalytic dynamic kinetic resolution (DKR) of chiral primary amines.
Article
Chemistry, Multidisciplinary
Luca Deiana, Abdolrahim A. Rafi, Veluru Ramesh Naidu, Cheuk-Wai Tai, Jan-E Backvall, Armando Cordova
Summary: The assembly of cellulose-based artificial plant cell wall structures with different types of catalysts is a powerful strategy for developing cascade reactions, such as transforming a racemic amine into enantiomerically pure amide in high yield by a dynamic kinetic resolution catalytic system containing a lipase enzyme and nanopalladium particles.
CHEMICAL COMMUNICATIONS
(2021)
