Article
Chemistry, Organic
Brock A. Miller, Chandima J. Narangoda, Thomas L. Johnson, Ryan D. Barata, Flavoris Belue, Erin E. Solomon, Alexis A. Bragg, Daniel C. Whitehead
Summary: In this study, we have overcome the challenge of modifying substituents and expanded the structural diversity of the diazacyclobutene scaffold.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Lilian Geniller, Marc Taillefer, Florian Jaroschik, Alexis Prieto
Summary: The Ni-photoredox catalyzed desulfurative cross-coupling reaction enables the synthesis of various unsymmetrical diarylmethane molecules under mild reaction conditions, providing new transformations of abundant, naturally occurring thiols.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Physical
Giulio Goti
Summary: This article discusses the application of catalytic radical methods in the functionalization of unsaturated carbohydrates, highlighting the opportunities they offer for new reaction design. These methods overcome the limitations of classical protocols and provide new routes for the synthesis of complex carbohydrates.
Article
Chemistry, Multidisciplinary
Yusuke Imamura, Kyohei Takaoka, Yuma Komori, Masanori Nagatomo, Masayuki Inoue
Summary: This study presents a 34-step synthesis of Taxol, involving inter- and intramolecular radical reactions to connect the A- and C-ring fragments and cyclize the B-ring. The A- and C-ring functional groups were then efficiently modified using newly developed selective reactions. The construction of the D-ring and its conjugation with the beta-amino acid led to the successful synthesis of Taxol. This synthesis provides useful insights for the design of multistep syntheses of diverse bioactive natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Thermodynamics
Akira Matsugi, Shunsuke Suzuki
Summary: The reaction pathways between propargyl and indenyl radicals, leading to the formation of acenaphthylene, were investigated. Quantum chemical methods were used to explore the potential energy surfaces for the reactions. Several reaction pathways for the formation of tricyclic species, which eventually produce acenaphthylene, were identified. The results indicate that acenaphthylene can be formed via three different routes, depending mainly on temperature. A simplified reaction mechanism for the major reaction pathways is proposed for kinetic modeling.
COMBUSTION AND FLAME
(2024)
Review
Biochemistry & Molecular Biology
Akiya Ogawa, Yuki Yamamoto
Summary: In this mini-review, we propose a concept for designing multicomponent reactions based on sequential radical reactions. We focus on the photolysis of interelement compounds to generate heteroatom-centered radicals and study their addition to unsaturated compounds. The background, basic concepts, and methodology for constructing multicomponent radical reactions are discussed, followed by examples of reactions involving different combinations of interelement compounds and unsaturated compounds, as well as intramolecular cyclization processes.
Article
Chemistry, Multidisciplinary
Kai Oberdorf, Anna Hanft, Jacqueline Ramler, Ivo Krummenacher, F. Matthias Bickelhaupt, Jordi Poater, Crispin Lichtenberg
Summary: The controlled release of aminyl radicals from bismuth amide species at ambient temperature enables selective N-N coupling reactions to yield hydrazines. Analyzes using various spectroscopy techniques and calculations reveal low homolytic bond-dissociation energies, suggesting radical coupling in the coordination sphere of bismuth, and demonstrate the effectiveness of electronic and steric parameters in controlling these reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Caroline J. Aschendorf, Mawuli Degbevi, Keaton V. Prather, Emily Y. Tsui
Summary: The participation of the surfaces of colloidal semiconductor nanocrystal quantum dots in QD-mediated photocatalytic reactions is crucial and should be considered in the design of photocatalysis. The study explores the reactivity of surface sulfides and selenides of metal chalcogenide QDs and demonstrates the importance of QD surfaces beyond tuning their band gaps.
Article
Chemistry, Multidisciplinary
Xinjie Yang, Hao Wang, Yanhua Zhang, Weike Su, Jingbo Yu
Summary: This study reports a method for the generation of radicals by directly breaking the C-N bonds of aryldiazonium salts using NaCl as an activator. This method enables various types of radical reactions and has been demonstrated to be practical and useful through scaling-up experiments, late-stage modification of pharmaceutical agents, and synthesis of bioactive compounds and pharmaceuticals.
Article
Food Science & Technology
Juan David Figueroa, Noreima Barroso-Torres, Marcela Morales, Barbara Herrera, Mario Aranda, Eva Dorta, Camilo Lopez-Alarcon
Summary: The ORAC assay does not differentiate between peptides based on their chemical structures and the contribution of oxidation products. Peptides showed similar ORAC values, but the bond dissociation energy (BDE) varied.
Article
Chemistry, Organic
Xiaoyu Chen, Bo Liu, Congcong Pei, Jingya Li, Dapeng Zou, Yangjie Wu, Yusheng Wu
Summary: A mild and efficient visible-light-induced radical difluoromethylation/cyclization of unactivated alkenes toward the synthesis of substituted quinazolinones with easily accessible difluoromethyltriphenylphosphonium bromide has been developed. The transformation has the advantages of wide functional group compatibility, a broad substrate scope, and operational simplicity, providing a facile access to pharmaceutically valuable difluoromethylated polycyclic quinazolinones.
Article
Chemistry, Medicinal
Junhui Lu, Huimin Zhang, Jinhui Yu, Dezun Shan, Ji Qi, Jiawen Chen, Hongwei Song, Minghui Yang
Summary: The study developed a machine learning approach to predict the temperature-dependent site-specific rate constants of hydrogen abstraction reactions, demonstrating robustness in accurately predicting the site-specific and overall rate constants.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Engineering, Environmental
Yangjian Zhou, Yu Lei, Qingqing Kong, Xin Lei, Jianglin Peng, Yufeng Xie, Shuangshuang Cheng, Yanpeng Gao, Junlang Qiu, Xin Yang
Summary: This study reported a novel pathway for the generation of sulfate radical (SO4 center dot-) during the oxidation of neonicotinoids by peroxydisulfate (PDS) without any additional chemicals. Thiamethoxam (TMX) was found to activate PDS via TMX anion radical (TMX center dot-), leading to the generation of SO4 center dot-. This pathway was also applicable to other neonicotinoids.
JOURNAL OF HAZARDOUS MATERIALS
(2023)
Review
Chemistry, Applied
Serena Pillitteri, Prabhat Ranjan, Erik V. Van der Eycken, Upendra K. Sharma
Summary: The chemistry of boron compounds has been extensively studied and applied in synthetic and biologically active molecules. The advent of photoredox catalysis has led to a surge in the discovery of suitable radical precursors, with boron playing a prominent role. However, the use of boronic acids and esters in photocatalyzed reactions has received less attention, and methods to enable their involvement have only recently been developed. Nonetheless, this review summarizes novel strategies to unlock their potential as radical precursors in photochemical reactions by exploiting their intrinsic chemical properties.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Johannes Koeckenberger, Insa Klemt, Caroline Sauer, Anton Arkhypov, Viktor Reshetnikov, Andriy Mokhir, Markus R. Heinrich
Summary: Despite their synthetic potential, radical thiol-yne coupling reactions have rarely been used to functionalize biomolecules, especially in live cells. However, by exploiting the cellular conditions of mitochondria in cancer cells, we have demonstrated the selective targeting of these organelles using this reaction principle.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
