Article
Chemistry, Physical
Caitlyn P. McNichol, Ethan M. DeCicco, Amanda M. Canfield, Daniel P. Carstairs, Shauna M. Paradine
Summary: We present a ligand-enabled, copper-catalyzed aerobic aminooxygenation reaction for internal alkenes. This transformation proceeds via an amidyl radical pathway, different from the previously established aminocupration pathway, through the synergistic combination of a phenanthroline-based ligand and substrate coordination. The switch in reaction mechanism leads to a broadened scope and accessibility to different substrate classes.
Article
Chemistry, Applied
Jinglei Yang, Yun-Dong Wu, Maoping Pu
Summary: A commercially available cobalt complex Cp*Co-III(CO)I-2 has been discovered to efficiently catalyze the diamination of α-alkyl styrenes with anilines under mild reaction conditions, using dioxygen as the oxidant. This reaction exhibits a reasonably wide substrate scope of amines and good functional group tolerance. Preliminary mechanistic studies have indicated that Cp*Co-III(CO)I-2 alone can facilitate the diamination reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Yu Li, Guo-Cui Ji, Chen Chao, Siwei Bi, Yuan-Ye Jiang
Summary: This study investigates the mechanism of Cu-catalyzed aerobic aminooxygenation of alkene-tethered amides through computational analysis. The results reveal that Cu(I) precursor is not the active species and the reaction is initiated by the formation of Cu(II) complexes. The study contributes to the understanding of Cu-catalyzed aerobic reactions.
Article
Chemistry, Physical
Yu Li, Guo-Cui Ji, Chen Chao, Siwei Bi, Yuan-Ye Jiang
Summary: This article reports a computational study on the mechanism of Cu-catalyzed aerobic aminooxygenation reactions. It was found that a Cu(I) precursor can generate two types of Cu(II) complexes to initiate the reactions. The first catalytic stage involves the conversion of alkene-tethered amides to alpha-amidated aldehydes, while the second stage involves the generation of imides from alpha-amidated aldehydes. The presented findings expand our understanding of Cu-catalyzed aerobic reactions and the role of different copper complexes.
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)
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
Junlin Li, Jinxian Liu, Chunling Fu, Shengming Ma
Summary: In this study, a combination of Fe(NO3)(3)center dot 9H(2)O/TEMPO/KCl catalysts was identified to efficiently catalyze the aerobic oxidation of 1,4-diols to yield gamma-butyrolactones under mild conditions. The reaction showed good chemo- and regioselectivity towards symmetrical and unsymmetrical 1,4-diols. Optically active gamma-lactones could also be obtained without loss of enantiomeric excess (ee) from optically active 1,4-diols using this method. Furthermore, this approach was successfully applied in the synthesis of the commercial drug NBP.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Rahul Kalita, Wahida Begum, Poorvi Gupta, Manav Chauhan, Naved Akhtar, Rajashree Newar, Kuntal Manna
Summary: This research reports on the synthesis and characterization of an aluminum metal-organic framework node-supported copper(II) chloride catalyst, which efficiently oxidizes alkenes to carbonyl or diol compounds using H2O2 as an oxidizing agent. The catalyst exhibits excellent selectivity and can be recycled, highlighting the importance of MOF-supported metal catalysts for oxidation reactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Ameya S. Burde, Sherry R. Chemler
Summary: Saturated heterocycles containing oxygen and sulfur are present in biologically significant molecules. This article presents a complementary approach using copper catalysis to synthesize enantioenriched compounds with high selectivity from acyclic alkenols.
Article
Chemistry, Physical
Zhiming Ma, Shiqiang Liu, Nanfang Tang, Tao Song, Ken Motokura, Zhemin Shen, Yong Yang
Summary: The coexistence of Fe nanoclusters and Fe single atoms in N-doped porous carbon can significantly enhance the catalytic performance in the aerobic oxidation of primary amines to imines.
Article
Biochemistry & Molecular Biology
Geert Watson, Parviz Gohari Derakhshandeh, Sara Abednatanzi, Johannes Schmidt, Karen Leus, Pascal Van der Voort
Summary: In this study, a highly N-rich covalent triazine framework (CTF) is utilized as a support for a Ru-III complex, which shows high catalytic performance in selective tandem aerobic oxidation-Knoevenagel condensation reaction. The obtained material not only serves as a catalyst support, but also provides active sites for both aerobic oxidation and Knoevenagel condensation reactions. This work demonstrates a new perspective for developing highly efficient and robust heterogeneous catalysts using CTFs for cascade catalysis.
Article
Chemistry, Inorganic & Nuclear
Irving D. Rettig, Kristine M. Halvorsen, Theresa M. McCormick
Summary: Tellurorhodamine dyes with different electron donating moieties were synthesized to study their photophysical properties and catalyst function. UV-Vis spectroscopy was used to determine the properties, and mass spectroscopy confirmed the oxidation of the dyes to telluroxides under visible light irradiation. Reduction studies showed that decreasing the electron density of the xylene moiety increased the rate of reduction.
DALTON TRANSACTIONS
(2023)
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, Multidisciplinary
Dahan Wang, Fuhong Xiao, Feng Zhang, Huawen Huang, Guo-Jun Deng
Summary: A copper-catalyzed aerobic oxidative ring expansion reaction has been developed for the synthesis of tetracyclic quinazolinones. The reaction proceeds smoothly under simple conditions, yielding moderate to good product yields with good functional group tolerance. The resulting 5H-isoquinolino[1,2-b]quinazolin-8(6H)-one has demonstrated a strong capacity for a range of palladium-catalyzed directing C-H activation, expanding the access to diverse tetracyclic quinazolinones.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Ping Fang, Tian-Sheng Mei, Zeng He, Hui-Lin Liu, Zhen-Hua Wang, Ke-Jing Jiao, Zi-Meng Li, Zhang-Jian Li
Summary: A method for the C(sp3)-H alkenylation of N-aryl-tetrahydroisoquinoline (THIQ) has been developed by the combination of electrooxidation and a copper catalyst. The corresponding products were obtained with good to excellent yields under mild conditions. Moreover, TEMPO addition as an electron mediator is crucial for this transformation, enabling the oxidative reaction to proceed under a low electrode potential. Additionally, the catalytic asymmetric variant has been demonstrated with good enantioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tomer M. Faraggi, Wei Li, David W. C. MacMillan
ISRAEL JOURNAL OF CHEMISTRY
(2020)
Article
Chemistry, Organic
Fan Wu, Jeewani P. Ariyarathna, Navdeep Kaur, Nur-E Alom, Maureen L. Kennell, Omar H. Bassiouni, Wei Li
Article
Chemistry, Organic
Fan Wu, Jeewani P. Ariyarathna, Nur-E Alom, Navdeep Kaur, Wei Li
Article
Chemistry, Organic
Nathan R. Gembreska, Alexander K. Vogel, Elizabeth C. Ziegelmeyer, Eric Cheng, Fan Wu, Leo P. Roberts, Megan M. Vesoulis, Wei Li
Summary: Iodonium catalysis is used in this study for intermolecular olefin oxyamination reaction, where urea is employed as the O- and N-source for regioselective addition onto both activated and unactivated alkenes. Mechanistic studies have confirmed the presence of an iodonium intermediate.
Article
Chemistry, Organic
Jeewani P. Ariyarathna, Nur-E Alom, Leo P. Roberts, Navdeep Kaur, Fan Wu, Wei Li
Summary: This study discloses practical strategies for the synthesis of morpholines and Claisen rearrangement products based on the divergent reactivity of a common halonium intermediate. By utilizing readily available alkenes in a Lewis acid-catalyzed halo-etherification process, exceptional regioselectivity is achieved for both activated and unactivated olefins. Additionally, a mechanistic probe reveals an interesting regiochemical kinetic resolution process.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
News Item
Chemistry, Multidisciplinary
Prabagar Baskaran, Wei Li
Article
Chemistry, Multidisciplinary
Jeewani P. Ariyarathna, Prabagar Baskaran, Akanksha Chhikara, Navdeep Kaur, Alex M. Nguyen, Shashini M. Premathilaka, Michelle M. Huynh, Jonathon T. Truong, Wei Li
Summary: We describe a diversified intermolecular coupling strategy that enables the direct synthesis of diverse N-heterocycles from olefins. The switching between radical and polar mechanisms is crucial for the divergent cyclization processes. These unique annulations involve the coupling of alkenes with simple bifunctional reagents for the synthesis of diverse N-heterocycles.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Navdeep Kaur, Elizabeth C. Ziegelmeyer, Olutayo N. Farinde, Jonathon T. Truong, Michelle M. Huynh, Wei Li
Summary: A catalytic benzylic C(sp)3-H functionalization protocol is described, utilizing a bromide catalyst and oxidant to generate a nitrogen (N)-centered radical for a site-selective hydrogen atom transfer (HAT) process under visible light-mediated condition. This strategy enabled unconventional syntheses of N-heterocycles based on the amide identity, and also discovered a nucleophilicity-dependent kinetic resolution for stereochemical differentiation of C(sp)3-H bonds, enabling the stereoselective synthesis of cis- and trans-oxazolines.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Fan Wu, Navdeep Kaur, Nur-E Alom, Wei Li
Summary: A novel iodide-catalyzed intermolecular aminooxygenation strategy is described, utilizing amide as the O- and N-source for regiocontrol. It was found that simple additives can selectively introduce regiodivergent oxyamination processes for electronically activated alkenes while being regio-complementary for unactivated alkenes. Preliminary data also suggests that this regiocontrol strategy can be applied in asymmetric processes using chiral hypervalent iodine catalysis.
Review
Chemistry, Organic
Navdeep Kaur, Fan Wu, Nur-E Alom, Jeewani P. Ariyarathna, Shannon J. Saluga, Wei Li
ORGANIC & BIOMOLECULAR CHEMISTRY
(2019)
Article
Chemistry, Organic
Jeewani Poornima Ariyarathna, Elizabeth Claire Ziegelmeyer, Wei Li
