Article
Chemistry, Organic
Anh Le, Daesung Lee
Summary: This study explores the substituent-dependent reactivity and selectivity in intramolecular reactions of arynes tethered with different allene isomers. It is found that the presence of 1,3-disubstituted allene favors an Alder-ene reaction over a [2 + 2] cycloaddition, while a 1,1-disubstituted allene prefers the [2 + 2] cycloaddition. Additionally, a 1,1,3-trisubstituted allene-tethered aryne shows preference for an Alder-ene reaction over a [2 + 2] cycloaddition.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
Helya J. Ghazvini, Hormoz Khosravi, Saber Mirzaei, Saeed Balalaie, Bernhard Breit
Summary: An innovative method for the selective formation of Z-vinyl-functionalized oxazoles via a rhodium-catalyzed nucleophilic addition of alpha-acidic isocyanoacetamides to allenes is described. By employing diverse isocyanoacetamides and allenes, a library of vinyl oxazoles can be efficiently synthesized in a stereo- and regiospecific manner. Mechanistic investigations reveal that the reaction proceeds through a concise rhodium-catalyzed ene reaction followed by reductive elimination.
Article
Chemistry, Applied
Hao Yuan, Dong-Liu Lu, Cui Liang, Dong-Liang Mo
Summary: Various spirooxindole-benzo[d]oxazoles and dihydrobenzofurans were successfully synthesized via transition metal-free [3 + 2] cycloaddition and selective rearrangement. The substituent on the N-vinyl group of the nitrone was found to control the [1,3]- or [3,3]-rearrangement of the cycloadduct due to steric effects. This method demonstrates broad substrate scope, good functional group tolerance, controllable rearrangement, and diverse oxindole scaffolds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yu Zhang, Yanchuan Li, Shao-Fei Ni, Jin-Peng Li, Dingding Xia, Xinyu Han, Jingchuan Lin, Jinxin Wang, Shoubhik Das, Wei-Dong Zhang
Summary: Visible-light-induced [3+2] cycloadditions of donor/donor diazo precursors with alkenes to afford pyrazoles and (spiro)pyrazolines have been reported. Mechanistic and DFT studies suggested the non-covalent interactions promote the reaction.
Article
Chemistry, Multidisciplinary
Yu Zhang, Yanchuan Li, Shao-Fei Ni, Jin-Peng Li, Dingding Xia, Xinyu Han, Jingchuan Lin, Jinxin Wang, Shoubhik Das, Wei-Dong Zhang
Summary: Visible-light-induced [3+2] cycloadditions of donor/donor diazo precursors with alkenes to afford pyrazoles and (spiro)pyrazolines have been reported. Mechanistic and DFT studies suggested the formation of non-covalent interactions promote the reaction.
Article
Chemistry, Organic
Alexey P. Krinochkin, Yaroslav K. Shtaitz, Aluru Rammohan, Ilya I. Butorin, Maria Savchuk, Igor A. Khalymbadzha, Dmitry S. Kopchuk, Pavel A. Slepukhin, Vsevolod V. Melekhin, Anna Shcheglova, Grigory Zyryanov, Oleg N. Chupakhin
Summary: An operationally simple and highly efficient one-pot method has been developed for the synthesis of pyridines appended with pyrazole via an NH linker. The synthesized compounds showed promising in silico activity against JAK1, SYK, and FAK1 kinases. In vitro testing demonstrated significant cytotoxicity of the most promising compound against A-172 and HepG2 cancer cell lines, with IC50 values below 50 μM. The in vitro anticancer activity correlates well with the predicted in silico data.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Maximilian Scheruebl, Constantin G. Daniliuc, Armido Studer
Summary: The article introduces the application of arynes as radical acceptors, showing how the stable radical TEMPO can react with different ortho-substituted benzynes to generate aryl radicals for subsequent cyclizations, eventually being trapped by TEMPO. This method provides a novel approach for the convenient synthesis of various dihydrobenzofurans, oxindoles, and sultones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Pedro H. R. Oliveira, Everton A. Tordato, Jeimy A. C. Velez, Pablo S. Carneiro, Marcio W. Paixao
Summary: Here, a rapid and scalable continuous-flow photocatalytic approach for the carbamoylation of nitrones is reported. This method utilizes readily available 4-amido-1,4 dihydropyridines as carbamoyl radical precursors. The transformation shows high compatibility with complex structures containing amino acids, peptides, and glycosides. It also enables a photocatalytic synthetic strategy combined with flow conditions, maximizing the potential and efficiency for the synthesis of valuable alpha-(N-hydroxy)-amino amides.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Medicinal
Satapanawat Sittihan, Pattarawut Sopha, Somsak Ruchirawat
Summary: Novel pentafluorobenzenesulfonamide derivatives with different molecular scaffolds were synthesized and evaluated for antitumor activities against multiple cancer cell lines. Dihydroimidazoline-containing analogues and their Diels-Alder cycloadducts showed enhanced cytotoxicity, while incorporation of other heterocyclic cores via nucleophilic substitution resulted in decreased potency. Selected analogues were found to induce apoptosis in cancer cells through caspase-dependent processes.
Review
Chemistry, Organic
Wang Junjiao, Lv Yuyu, Shang Yongwei, Cui Zhenli, Wang Ke-Hu, Huang Danfeng, Hu Yulai
Summary: This article summarizes the nucleophilic addition reactions and cycloaddition reactions involving alpha-hydroxyl ketones. Alpha-hydroxyl ketones are not only key structural fragments of many natural products, but also important building blocks for the synthesis of biologically active molecules and drugs.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Xiaoqing Xiong, Ye Yuan, Gengwen Chen, Miao Li, Lihua Lyu, Hongjuan Zhao, Jun Yan, Yulan Qian, Junyang Zhu, Chengqi Jiao
Summary: The investigation on the construction strategy and relationship between the structure and photophysical properties of fluorescein analogs is important for the design of specific fluorescent dyes.
Article
Biochemical Research Methods
Anthony Fosu, George Baffour Pipim, Richard Tia, Evans Adei
Summary: The research indicates that the reaction between nitrone derivatives and allenoates tends to proceed through the initial (3+2) cycloaddition route both kinetically and thermodynamically, instead of the initial oxygen-nucleophilic addition. Increasing steric bulk can bridge the gap between the two reactions, but the (3+2) cycloaddition remains energetically preferred.
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
(2021)
Review
Chemistry, Organic
Wenhao Yuan, Jiaxi Xu
Summary: Oxetanes are important small heterocycles widely used in organic, pharmaceutical, and polymer chemistry, with a preference for ring-opening and ring expansion reactions to construct various oxygen-containing large heterocyclic compounds. This review discusses the different ring expansion reactions of oxetanes and their reaction mechanisms, while also proposing new prospects for future development.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jiupeng Liu, Shuo Tang, Mengyao Zhao, Jianing Huai, Jingya Yu, Jingjing Zhao, Pan Li
Summary: The reactivity of vinyl epoxides/oxetanes/cyclopropanes towards arynes can lead to the synthesis of various functionalized phenanthrenes under mild conditions. This transition-metal-free cascade process involves a series of Diels-Alder reaction, ring-opening aromatization, and ene reaction. Vinyl epoxides/oxiranes show a preference for Diels-Alder reaction with arynes over nucleophilic attack.
Article
Chemistry, Physical
Cheng Cai, Weiqiang Tang, Chongzhi Qiao, Bo Bao, Peng Xie, Shuangliang Zhao, Honglai Liu
Summary: This article investigates the solvent effects on nucleophilic addition reactions in aqueous solution using the proposed multiscale reaction density functional theory (RxDFT) method. The results provide a better understanding of the mechanism and the solvent effect on chemical reactions, especially those occurring at solid-liquid interfaces.
GREEN ENERGY & ENVIRONMENT
(2022)
