Article
Chemistry, Organic
Qin Yang, Zhe Wang, Terumasa Kato, Yan Liu, Keiji Maruoka
Summary: Alkyl tert-butyl peroxides are synthesized from their corresponding tert-alkyl precursors and tert-butyl hydroperoxide with the aid of a promoter. These peroxides can be used in a copper-catalyzed radical functionalization, which involves coupling with various partners and exhibits broad substrate compatibility. Mechanistic investigations suggest the involvement of alkyl radical species in the coupling reactions.
Review
Chemistry, Organic
Bo-Ya Hao, Ya-Ping Han, Yuecheng Zhang, Yong-Min Liang
Summary: Fluorinated organic compounds, especially those containing the OCF3 group, are of great importance in various fields. In recent years, the synthesis of trifluoromethoxylated compounds has attracted much attention, and different strategies have been developed for their efficient and practical synthesis. These strategies involve de novo formation of the OCF3 group, trifluoromethylation of alcohols or phenols, direct installation of the OCF3 group onto complex molecules, visible-light-induced trifluoromethoxylation, transition metal-catalyzed trifluoromethoxylation, and rearrangement reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Agnieszka Mikus, Beata Lopuszynska
Summary: This review discusses nitration reactions of porphyrin derivatives and their importance in providing valuable intermediates for further transformations. The introduction of NO2 group increases the electrophilic character of porphyrins, leading to a broad spectrum of subsequent reactions. This approach allows synthesizing complex porphyrin-like compounds, with nitration substitutions possible at various positions in the porphyrin systems.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Organic
Zhuyong Zhang, Junfei Luo, Hongyin Gao
Summary: A new strategy for the synthesis of fluorinated anilides without the use of metals and oxidants has been developed, resulting in moderate to good yields of ortho- or para-fluorinated aromatic amine products. This method allows for the efficient construction of structurally diverse fluorinated anilides, including heterocyclic and pharmaceutically relevant molecules.
Article
Environmental Sciences
Yanhui Sun, Lin Liu, Ming Li, Xiaoxiao Chen, Fei Xu
Summary: Vanillin and vanillic acid are two lignin pyrolysis products generated by biomass combustion. The gas-phase oxidation mechanisms of vanillin and vanillic acid initiated by OH/NO3 radicals were investigated using density functional theory. The primary reactions involve OH/NO3 addition and H-atom abstraction, leading to the formation of various oxidation products. The total rate constants and atmospheric lifetimes of the oxidation processes were calculated, providing valuable information for further experimental research.
Review
Chemistry, Physical
Tomasz Klis
Summary: Fluorine-containing functional groups play a crucial role in the physical and biological properties of organic compounds. Visible-light photoredox catalysis has emerged as a powerful strategy for the introduction of fluorine atoms into organic substrates, leading to the rapid development of new synthetic procedures. This review highlights different strategies for transition metal- and organic-photocatalytic fluorination of arenes and heteroarenes using a wide range of fluorinating compounds. The presented procedures can be divided into two groups: direct attachment of different fluorine-containing substituents to aromatic compounds, and tandem reactions where aromatic systems are formed after installation of fluorine-containing groups on the non-aromatic fragment of the molecule.
Article
Chemistry, Organic
Xiaoyun Deng, Ziqiang Wang, Huimin Zhou, Junyi Liu, Bo Yu, Xiaohua Zhu
Summary: A new method was developed to directly construct aryl-SO2-18F from arenediazonium tosylates using a SO2 source and [18F]fluoride. This approach is compatible with various substrates and allows for the production of 18F-labeled drug-like derivatives through late-stage 18F fluorination, representing a significant advancement in the radiosynthesis of 18F-labeled arenesulfonyl fluorides. Additionally, a reactive 18F labeling synthon with a maleimide-based prosthetic group enables the generation of 18F-labeled temperature-sensitive biomolecules containing cysteine residues through maleimide-cysteine chemistry.
Article
Chemistry, Organic
Kevin Renault, Romain Horion, Xavier Maes, Maha Rzeigui, Yoann Joyard, Nicolas Maindron, Vincent Tadino, Stephane Vincent
Summary: In this article, a general method based on a central Mitsunobu reaction is reported to access 2-nitroimidazole precursors for the radiofluorination of PET tracers used in non-invasive hypoxic tumor diagnosis. Additionally, a new potential hypoxia PET tracer is synthesized and an SFC analytical method is presented for monitoring fluorination reactions and measuring partition coefficients (logP).
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ryohei Doi, Koki Kajiwara, Taiki Negoro, Kenta Koh, Sensuke Ogoshi
Summary: In this study, a nickel-catalyzed cross-coupling reaction was developed for the synthesis of alkenylNi complexes by cleaving C-F bonds of silyl difluoroenolates using aryl zinc reagents. The reaction selectively delivered a single geometric isomer of a fluoroenolate by using a stoichiometric amount of Ni(0)/N-heterocyclic carbene (NHC) and a lithium salt. This work provides a valuable method for the construction of complex fluorinated molecules.
Article
Chemistry, Multidisciplinary
Helian Li, Yongxin Zhang, Xiaoxiao Yang, Zhenxi Deng, Zhimin Zhu, Pan Zhou, Xinke Ouyang, Yuting Yuan, Xi Chen, Lingyue Yang, Meng Liu, Chao Shu
Summary: This study reports a photoredox-catalyzed multifluoromethyl radical addition/SO2 incorporation/polar cyclization cascade approach for the synthesis of multifluoromethylated gamma-sultines. The reactions proceed by single electron transfer induced multifluoromethyl radical addition to an alkene followed by SO2 incorporation and single-electron reduction for polar 5-exo-tet cyclization. The use of easily oxidizable multifluoroalkanesulfinates as bifunctional reagents is key to the success of this protocol. The reactions exhibit excellent functional-group tolerance and deliver gamma-sultines in moderate to excellent yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Roy Arun, Sebastian Stiniya, Padinjare Veettil Saranya, Gopinathan Anilkumar
Summary: This review provides an overview of various Pd-catalyzed trifluoromethylation reactions up to 2021, highlighting their significant applications in organofluorine chemistry and the broad functional group tolerance and good selectivity of palladium catalysts.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Review
Polymer Science
Guoqiang Liu, Ruihao Pan, Yen Wei, Lei Tao
Summary: The Hantzsch reaction is a powerful tool for synthesizing 1,4-dihydropyridine derivatives, and has recently been introduced into polymer chemistry for developing polymers with new functions. These polymers with 1,4-DHP structures have potential applications in various fields. The future development of the Hantzsch reaction is promising for exploring new functional polymers.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Review
Crystallography
Weiqing She, Zhenzhen Xu, Lianjie Zhai, Junlin Zhang, Jie Huang, Weiqiang Pang, Bozhou Wang
Summary: Due to the introduction of oxygen atoms, N-oxide energetic compounds possess unique advantages in terms of oxygen balance, detonation properties, and energy density, which have attracted extensive attention from researchers worldwide. This article provides a comprehensive review of the synthetic strategies for two categories of N-oxides, azine N-oxides and azole N-oxides, and discusses the reaction mechanisms of aromatic N-oxide frameworks and their applications in creating high-energy substances. Furthermore, the energetic properties of N-oxide energetic compounds are compared and summarized.
Article
Chemistry, Multidisciplinary
Jay S. Wright, Liam S. Sharninghausen, Sean Preshlock, Allen F. Brooks, Melanie S. Sanford, Peter J. H. Scott
Summary: This article presents a novel method for the meta-selective C-H radiofluorination of (hetero)arene substrates. The process can be conducted on a benchtop without the need for Schlenk or glovebox techniques, resulting in higher yields and purity of the products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Marc Magre, Shengyang Ni, Josep Cornella
Summary: This review evaluates and summarizes the progress in the synthesis of highly fluorinated aryl-S-VI compounds at all levels, discussing synthetic strategies, reactivity, the advantages and disadvantages of the synthetic procedures, the proposed mechanisms, and the potential upcoming opportunities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Craig E. Stival, Jason R. Zbieg, Peng Liu, Michael J. Krische
Summary: This article presents the research on the amination reaction catalyzed by pi-allyliridium-C,O-benzoate complexes. The experimental results show that this catalytic system can achieve highly stereoselective amination reactions and can be applied to various types of amines and nitronates. The study also reveals the mechanism of these reactions and the origin of the stereoselectivity.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Organic
Daniel P. Dempe, Chong-Lei Ji, Peng Liu, Kay M. Brummond
Summary: This study synthesized a series of N-aryl-substituted alpha-methylene-gamma-lactams within the framework of a bioactive guaianolide analog. The effects of the guaianolide structure on the electrophilic reactivity were investigated by reacting these compounds with glutathione and measuring rate constants. The trans-annulated compounds showed approximately a 10-fold increase in reactivity compared to the cis annulated compounds and the corresponding N-arylated 3-methylene-2-pyrrolidinones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yue Fu, Heyu Chen, Wenzhen Fu, Marc Garcia-Borras, Yang Yang, Peng Liu
Summary: New-to-nature radical biocatalysis has emerged as a powerful strategy for stereoselective transformations, with a novel metalloredox biocatalysis leveraging the heme cofactor of P450 enzymes to enable excellent activity and stereoselectivity. Computational and experimental studies shed light on the mechanism and enantioselectivity origins, revealing a bifunctional ATRCase with unexpectedly beneficial mutation I263Q enhancing radical cyclization enantioselectivity through a hydrogen bond donor residue.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yuhua Jiang, Harrison M. Snodgrass, Yasmine S. Zubi, Caitlin V. Roof, Yanfei Guan, Dibyendu Mondal, Nicholas H. Honeycutt, Johnny W. Lee, Russell D. Lewis, Carlos A. Martinez, Jared C. Lewis
Summary: This study establishes that the single component flavin reductase/flavin dependent halogenase AetF can catalyze halogenation of a diverse set of substrates using a commercially available glucose dehydrogenase. The AetF enzyme shows high site selectivity, activity on relatively unactivated substrates, and high enantioselectivity for atroposelective bromination and bromolactonization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Colton R. Davis, Yue Fu, Peng Liu, Joseph M. Ready
Summary: This article investigates the catalytic role of iridium (phosphoramidite) complexes in a three-component coupling reaction and reveals its mechanism and selectivity. Analyzing the stereochemistry of the products provides insight into the transition state and concerted pathway of the addition. Kinetic analysis reveals the order dependence of the reaction. Comparison with other nucleophiles is made by studying the parameters of the alkenyl boronate complexes. DFT calculations show that the mechanism of the reaction is concerted and the stereoselectivity is determined by ligand-substrate steric repulsions and dispersion interactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Ruihan Wang, Yidong Wang, Ruiqi Ding, Parker B. Staub, Christopher Z. Zhao, Peng Liu, Yi-Ming Wang
Summary: A newly-developed cationic cyclopentadienyliron dicarbonyl complex enables the conversion of propylene to its allylic C-C bond coupling products under catalytic conditions. This approach is also applicable to the allylic functionalization of simple alpha-olefins with distinctive branched selectivity. Experimental and computational studies reveal the allylic deprotonation of the metal-coordinated alkene as the turnover-limiting step and provide insights into the multifaceted roles of the newly designed ligand in promoting allylic C-H functionalization with enhanced reactivity and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tobias Koengeter, Can Qin, Binh Khanh Mai, Qinghe Liu, Yucheng Mu, Peng Liu, Amir H. Hoveyda
Summary: This paper presents a stereoretentive strategy for catalytic cross-metathesis reaction between tri-, Z- or E-di, or monosubstituted olefins and Z- or E-2-bromo-2-butene, leading to the formation of various trisubstituted alkenyl bromides. The method is applicable for the generation of products containing polar moieties or sterically hindered alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Amit Kumar Simlandy, Turki M. Alturaifi, Johny M. Nguyen, Lucas J. Oxtoby, Quynh Nguyen Wong, Jason S. Chen, Peng Liu, Keary M. Engle
Summary: We report a transient directing group (TDG) strategy for site-selective palladium-catalyzed reductive Heck-type hydroalkenylation and hydroalkynylation of alkenylaldehydes using alkenyl and alkynyl bromides. This strategy allows for the construction of a stereocenter at the delta-position with respect to the aldehyde. Computational studies reveal the beneficial roles of rigid TDGs, such as L-tert-leucine, in promoting TDG binding and inducing high levels of enantioselectivity in alkene insertion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hui-Qi Ni, Malkanthi K. Karunananda, Tian Zeng, Shenghua Yang, Zhen Liu, K. N. Houk, Peng Liu, Keary M. Engle
Summary: Multistep organic synthesis allows the conversion of simple chemical feedstocks into more complex products with specific functions. This study introduces a novel approach to organic reactions that can generate multiple valuable products with different carbon skeletons in a single operation. Through a palladium-catalyzed reaction, a single alkene starting material can be converted into two structurally distinct products, demonstrating the potential for simultaneous access to diverse compounds. The findings of this study provide insights into the mechanistic details of this unique catalytic system and establish a new method for small-molecule library synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jingfeng Huo, Yue Fu, Melody J. Tang, Peng Liu, Guangbin Dong
Summary: In this research, the first nickel-catalyzed Catellani-type annulation of aryl triflates and chlorides was achieved to form various benzocyclobutene-fused norbornanes in high efficiency. Mechanistic studies revealed an unexpected outer-sphere concerted metalation/deprotonation pathway and the essential roles of the base and the triflate anion. Compared to palladium catalysis, the reaction showed a broad functional group tolerance and enhanced regioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Christophe Allais, Christina G. Connor, Nga M. Do, Samir Kulkarni, Johnny W. Lee, Taegyo Lee, Emma McInturff, Jared Piper, Dave W. Place, John A. Ragan, R. Matt Weekly
Summary: The novel coronavirus, SARS-CoV-2, which caused a pneumonia outbreak in Wuhan, China in 2019, showed a close similarity to the SARS-CoV-1 virus. Pfizer identified a potential antiviral therapy, PF-07321332 (nirmatrelvir), which inhibits the replication of SARS-CoV-2. The successful development of this drug allowed for FDA emergency use authorization within just 17 months.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Jicheng Wu, Peijing Jia, Rositha Kuniyil, Peng Liu, Weiping Tang
Summary: In this study, we report an efficient method for the stereoselective synthesis of challenging α-linked glycoconjugates using a Rh-II/chiral phosphoric acid (CPA)-cocatalyzed dynamic kinetic anomeric O-alkylation. By exploring various parameters of the cocatalytic system, we achieved excellent anomeric selectivity, excellent diastereoselectivity, broad substrate scope, and high efficiency for this glycosylation reaction. DFT calculations suggested that the anomeric selectivity was determined by steric interactions between the C2-carbon of the carbohydrate and the phenyl group of the metal carbenoid, while diastereoselectivity at the newly generated stereogenic center was influenced by π-π interactions with the C2-OBn substituent on the carbohydrate substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dennis A. Kutateladze, Binh Khanh Mai, Yuyang Dong, Yu Zhang, Peng Liu, Stephen L. Buchwald
Summary: A copper hydride-catalyzed approach has been developed for the synthesis of Z-configured trisubstituted alkenes with high stereo- and regioselectivity. This method provides a valuable strategy for accessing challenging classes of alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Lei Cheng, Dian Li, Binh Khanh Mai, Zhiyu Bo, Lida Cheng, Peng Liu, Yang Yang
Summary: The merger of photoredox catalysis and PLP biocatalysis enables the development of a new synthetic method for preparing valuable noncanonical amino acids, allowing controlled formation of chiral products.
Article
Chemistry, Physical
Wenzhen Fu, Natalia M. M. Neris, Yue Fu, Yunlong Zhao, Benjamin Krohn-Hansen, Peng Liu, Yang Yang
Summary: This study describes a metalloredox biocatalysis strategy to repurpose natural cytochromes P450 for catalysing asymmetric radical cyclization to arenes through an unnatural electron transfer mechanism. Directed evolution yielded a series of engineered P450 aromatic radical cyclases with complementary selectivities. The excellent tunability of this metalloenzyme family provides an exciting platform for utilizing free radical intermediates in asymmetric catalysis.
