Article
Chemistry, Applied
Tai-Gang Fan, Xue-Ling Ding, Bo-Xun Sun, Yu-Jian Hou, Bo Jiang, Xu-Nan Wang, Ya-Min Li
Summary: A radical bicyclization of 2-cyanoaryl acrylamides with dicumyl peroxide has been developed to construct a broad spectrum of benzo[h]naphtho[1,8-bc][1,6]naphthyridine. This reaction involves the formation of three new chemical bonds through addition of methyl radical across alkene double bond, intramolecular addition of carbon-centered radical to cyano group, and cyclization of the iminyl radical cascade. It features a simple reaction system and wide substrate scope.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Chixiao Ma, Jingli Xie, Xianghua Zeng, Zheyu Wei, Yongge Wei
Summary: A direct carboselenation method for terminal alkynes using diorganyl diselenides and azobisisoalkylcarbonitriles via radical process has been developed. It provides excellent regioselectivity and stereoselectivity, and features catalyst- and additive-free conditions with less toxic cyanating sources and broad substrate generality.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Qianding Zeng, Ying Liu, Jingjing He, Yupian Deng, Pai Zheng, Zhudi Sun, Song Cao
Summary: A practical and efficient solvent-free synthesis of beta-trifluoromethyl-substituted phosphonates and phosphine oxides via hydrophosphonylation and hydrophosphinylation of alpha-(trifluoromethyl)styrenes with H-phosphonates and H-phosphine oxides, respectively, was developed. The reaction proceeded smoothly within 2 h at room temperature without the cleavage of the rather fragile C-F bond in alpha-(trifluoromethyl)styrenes and afforded a wide variety of structurally diverse and valuable beta-trifluoromethyl-containing phosphonates and phosphine oxides in moderate to good yields. This protocol features mild conditions, wide substrate scope, simple manipulation, and excellent functional group compatibility.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kensuke Kiyokawa, Miu Ishizuka, Satoshi Minakata
Summary: This study reports on the intermolecular oxycyanation of alkenes using p-toluenesulfonyl cyanide (TsCN) and tris(pentafluorophenyl)borane (B(C6F5)3) as a catalyst, which affords products containing a sulfinyloxy group and a cyano group at the vicinal position. The reaction exhibits stereospecific syn-addition and a broad substrate scope with good functional group tolerance. Mechanistic investigations reveal that the reaction proceeds through an unprecedented stereospecific mechanism involving electrophilic cyanation of alkenes and coordination of the cyano group to the boron center.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Shihao Li, Chenglong Zheng, Sheng Wang, Xiao-Xuan Li, Qi Zhang, Shilu Fan, Yi-Si Feng
Summary: A novel three-component alpha-acylated difunctionalization strategy has been developed using a direct hydrogen atom transfer process of photoinduced acyl azolium salts. Various olefins can be directly converted into ketone derivatives, including 1,4-dione, beta-silyl ketone, 1,5-dione, etc., with simple irradiation without the need for a catalyst.
Letter
Chemistry, Organic
Nicholas J. Venditto, Jeffrey A. Boerth
Summary: Multicomponent radical polar crossover (RPC) reactions are powerful tools for efficient synthesis of molecules with high complexity. However, little research has been done on multicomponent RPC reactions using carbonyl pi-bond electrophiles. In this study, a mild and photoredox-catalyzed decarboxylative multicomponent RPC reaction was developed to synthesize diverse gamma-amino butyric acid derivatives. This reaction also enables the synthesis of complex and biologically relevant gamma-lactam compounds.
Article
Chemistry, Organic
Xiaoyu Zhang, Yinlei Zhang, Xiaohong Li, Bowen Li, Shiji Xiao, Yongming Tang, Peizhong Xie, Teck-Peng Loh
Summary: This study presents a novel organophotoredox/DABCO catalytic system for the fluoroalkylation of activated allylic acetates via radical-radical coupling. The method offers mild reaction conditions, high selectivity, and broad substrate compatibility, allowing for the incorporation of diverse bioactive molecules, FDA-approved drugs, and amino acid derivatives. This expands the synthetic toolbox for the construction of fluorine-containing molecules.
Article
Chemistry, Organic
Changyou Guo, Lijun Li, Qinqin Yan, Hongxun Zhou, Zhong-Quan Liu, Zejiang Li
Summary: A photopromoted cyanomethylation/cyclization reaction of aryl acetylenes/ethylenes with bromoacetonitrile was developed, providing an efficient and mild protocol for the synthesis of cyanomethylated 7- or 5-membered N-heterocycles in good yields. Trichloroacetonitrile was also compatible with this radical pathway. The tandem system exhibited excellent performance in various aspects, including single-crystal X-ray diffraction measurements, scaled-up operations, functional group transformations, light on/off experiments, and radial inhibition studies.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chaorui Ma, Jingyu Shen, Chaofan Qu, Tianju Shao, Shanshan Cao, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: Chemodivergent synthesis is achieved in asymmetric photocatalysis using a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer. Different inorganic bases enable the formation of valuable products from the three-component radical tandem transformations. The distinct pKa environment plays a key role in the success of this process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chaorui Ma, Jingyu Shen, Chaofan Qu, Tianju Shao, Shanshan Cao, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: Chemodivergent synthesis was achieved using asymmetric photocatalysis. By using a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer, different inorganic bases were used to enable the formation of two sets of valuable products from a three-component radical tandem transformation. The key to success was the distinct pK(a) environment, which determined the fate of the radicals formed on the quinoxalin-2(1H)-one rings.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Zequn Yang, Longhui Chen, Qi Sun, Minjie Guo, Guangwei Wang, Wentao Zhao, Xiangyang Tang
Summary: A novel tetrahydroxydiboron and nickel chloride cocatalyzed radical cyclization cascade reaction with a broad substrate scope and ultrashort reaction time was developed. The mechanistic investigation suggested that the reaction might involve homocleavage of tetrahydroxydiboron and nickel hydride intermediates. This method enables the simple and efficient synthesis of a series of heteropolycycles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Benxiang Zhang, Jiayan He, Yi Li, Tao Song, Yewen Fang, Chaozhong Li
Summary: Acylphosphonates with the 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton have been developed as efficient intermolecular radical acylation reagents for cobalt-catalyzed Markovnikov hydroacylation of unactivated alkenes at room temperature. The protocol shows broad substrate scope and good functional group compatibility, providing satisfactory yields of branched ketones. The proposed mechanism involves Co-H mediated hydrogen atom transfer and subsequent trapping of alkyl radicals by acylphosphonates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Wen-Jun Han, Jian-Wu Zhang, Chao-Xian Yan, Jia-Wei Wang, Pan-Pan Zhou, Bing Han
Summary: A radical [1,4]-oxygen-atom transfer has been achieved through the reaction of linear alkyne-tethered ketoximes and ethynylbenziodoxolones (EBX) under sequential catalytic conditions. Mechanistic studies reveal a cascade process involving O atom radical cyclization, alkynylation, N-O bond photocleavage, and subsequent N,O-diradical rearrangement. By varying the catalytic sequences, a series of structurally important 3H-pyrrol-3-ones and chlorinated furo[3,2-b]pyrroles were synthesized, accompanied by an O atom shift, using Cu/Ir photosensitization and Cu/Ir photosensitization/AlCl3 catalysis, respectively.
Article
Chemistry, Organic
Fei Cheng, Li-Li Wang, Yuan-Hu Mao, Yong-Xi Dong, Bin Liu, Gao-Feng Zhu, Yuan-Yong Yang, Bing Guo, Lei Tang, Ji-Quan Zhang
Summary: An efficient aerobic iron-catalyzed annulation method for unsaturated carboxylic acids with disulfides has been developed, providing practical access to a wide range of substituted gamma-lactone derivatives. The disclosed method is simple, highly atom-economic, environmentally friendly, and tolerates a broad substrate scope.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jiajia Yu, Xu Zhang, Xinxin Wu, Tao Liu, Zhi-Qi Zhang, Jie Wu, Chen Zhu
Summary: Due to its simplicity, ethylene, as the most abundant organic feedstock, has limited applications in fine chemical synthesis, leading to the formation of molecules with modest complexity. Ethylene difunctionalization allows for the synthesis of more complex chemicals, but it is rare and typically relies on transition-metal catalysis. In this study, a novel metal-free radical difunctionalization of ethylene through functional group migration strategy is reported. The use of sulfone-based bifunctional reagents enables straightforward access to a wide range of diheteroarylated compounds under mild conditions in a highly selective manner, facilitated by the precise modulation of radical polarity and kinetic preference arising from intramolecular functional group migration.
Review
Chemistry, Physical
Bert Biesemans, Jeriffa De Clercq, Christian V. Stevens, Joris W. Thybaut, Jeroen Lauwaert
Summary: Aminated materials play a crucial role as aldol condensation catalysts, facilitating the reaction through an enamine mechanism. The reaction environment and the addition of small amounts of water are important factors. The development of water tolerant (bio)polymer supported amine catalysts has opened up opportunities for further catalyst development.
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING
(2022)
Review
Chemistry, Multidisciplinary
Lucas Mele, Jean Luc Pirat, Tahar Ayad, David Virieux
Summary: This comprehensive review summarizes the significant progress made in the synthesis of alkynylphosphorus compounds over the past 20 years. It focuses on sustainable catalysis or direct metal-free couplings from stable precursors. The review provides detailed insights into recent advancements and mechanisms of metal-catalyzed reactions, photocatalytic reactions, and metal-free reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Kmar Abaid, William Erb, David Virieux, Laurent Picot, Benjamin Musnier, Valerie Thiery, Thierry Roisnel, Florence Mongin, Soufiane Touil
Summary: An efficient and simple method was developed for the synthesis of unprecedented 4,5-diphosphonyldihydropyridazines and 3,4-diphosphonylpyrroles. The reactions proceeded under operationally simple, mild, and catalyst-free conditions, and showed promising growth inhibition against melanoma cancer cells.
Article
Nanoscience & Nanotechnology
Kuber Singh Rawat, Sander Borgmans, Tom Braeckevelt, Christian V. V. Stevens, Pascal Van Der Voort, Veronique Van Speybroeck
Summary: Two-dimensional nanoporous covalent organic frameworks (2D COFs) have attracted significant interest due to their wide range of applications. Understanding the layer stacking in 2D COFs and its effect on the structural and electronic properties is crucial. In this study, a detailed density functional theory investigation was carried out on four materials, revealing the optimal slipped AA-stacking configuration and the importance of considering dynamic fluctuations in accurately modeling the stacking configuration. The electronic band structure of COFs was found to be profoundly affected by different stacking configurations, with a decrease in layer offset leading to increased interlayer charge mobility.
ACS APPLIED NANO MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Aija Trimdale-Deksne, Artis Kons, Liana Orola, Anatoly Mishnev, Dmitrijs Stepanovs, Liliana Mazur, Magdalena Skiba, Marta K. Dudek, Nicolas Fantozzi, David Virieux, Evelina Colacino, Agris Berzins
Summary: This study investigates the factors contributing to the formation of polymorphs, hydrates, solvates, and solvate hydrates in three hydantoin-based active pharmaceutical ingredients-nitrofurantoin, furazidin, and dantrolene. Crystallographic and computational analysis of the crystal structures of these compounds reveals differences in their hydrogen bonding patterns and packing features, which correlate with their propensity to form solvates and solvate hydrates. The stability of the hydrate phases also plays a role in the differences observed.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Bert Biesemans, Noor Aljammal, Sambhu Radhakrishnan, Eric Breynaert, Christian V. Stevens, Jeroen Lauwaert, Joris W. Thybaut
Summary: The development of a high-performing aminated catalyst requires the adjustment of interactions between the active site, support, and solvent system. In this study, a pyrrolidine group was immobilized on a swellable polymer resin, leading to favorable interactions between the support and water as a solvent. Despite potential inhibition from iminium species, the catalyst exhibited a high turnover frequency. The solvent's affinity for the support resulted in efficient swelling, which was crucial for the observed catalytic performance.
Article
Chemistry, Multidisciplinary
Lucas Mele, Rachida Babouri, Jean-Luc Pirat, Eder Tomas-Mendivil, David Martin, Tahar Ayad, David Virieux
Summary: In the past 30 years, researchers have shown great interest in synthesizing atropochiral biaryls with steric congestion on the ortho-substituted arenes. This study presents an efficient approach to produce a new class of 2,2' disubstituted biaryls bridgehead phosphine oxides with exceptional conformational stability. The researchers found that by replacing only one hydrogen atom at the ortho position with a fluorine atom, the rotation of the biaryl backbone can be restricted at temperatures below 80°C, significantly extending the limits of atropostability. Additionally, their investigations revealed unique insights into the isomerization mechanism of these molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Simon Backx, Andreas Dejaegere, Andreas Simoens, Jef Van de Poel, Dorota Krasowska, Christian V. Stevens, Sven Mangelinckx
Summary: Organophosphorus compounds like phosphonamidates have applications in pharmaceuticals and pesticides but their synthesis is challenging. We present a flexible, room temperature synthesis for novel P-alkylphosphonamidates that avoids the need for intermediary purification. Our method utilizes oxalyl chloride and phosphonylaminium salts to catalyze the reactions of phosphonochloridates, resulting in the desired products. This protocol is compatible with primary and secondary amines and various phosphonate esters, and it offers a cheap and safe alternative for ammonia in the synthesis of primary phosphonamidates.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Melike Pala, Sophie L. K. W. Roelants, Wim Soetaert, Christian V. Stevens
Summary: Sophorolipids are attractive microbial biosurfactants with surface-active and biological properties. However, their commercialization has been limited due to minimal structural variation via fermentation. Chemical modification of sophorolipids allows for the generation of derivatives, enabling a fundamental understanding of structure-activity relationships and high-value applications. This review provides an overview of recent developments in chemical modification and targeted applications of sophorolipids and related microbial glycolipids.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Plant Sciences
Yinwei Zeng, Inge Verstraeten, Hoang Khai Trinh, Robin Lardon, Sebastien Schotte, Damilola Olatunji, Thomas Heugebaert, Christian Stevens, Mussa Quareshy, Richard Napier, Sara Paola Nastasi, Alex Costa, Bert De Rybel, Catherine Bellini, Tom Beeckman, Steffen Vanneste, Danny Geelen
Summary: This study reveals the molecular processes involved in the initiation of adventitious root (AR) formation along the hypocotyl of Arabidopsis seedlings exposed to light. The results show that AR induction by HYSPARIN involves nuclear TIR1/AFB and plasma membrane TMK auxin signaling, as well as multiple downstream LR development genes. Additionally, SAUR19, OFP4, and AGC2 are identified as novel regulators of AR formation.
Article
Chemistry, Multidisciplinary
Casper Van Poucke, Aurele Vandeputte, Sven Mangelinckx, Christian V. Stevens
Summary: In the transition towards the use of renewable resources, using biopolymers with desirable functionalities, such as chitosan derived from natural chitin, is advantageous. However, chitosan's limited solubility in plain water at neutral pH poses a challenge for its biological applicability. Here, we present a green and efficient method to make chitosan plain water-soluble without the need for acidic conditions.
Article
Chemistry, Multidisciplinary
Jonas Everaert, Karen Leus, Hannes Rijckaert, Maarten Debruyne, Kristof Van Hecke, Rino Morent, Nathalie De Geyter, Veronique Van Speybroeck, Pascal Van Der Voort, Christian V. Stevens
Summary: Covalent triazine frameworks (CTFs) based on polydentate ligands are promising catalyst supports that combine the reactivity of homogeneous catalysts with the robustness and recyclability of heterogeneous ones. In this study, a rhodium (III) complex was immobilized on a bipyridine-based CTF for the transfer hydrogenation of N-heteroarenes in water using sodium formate as the hydrogen source. The immobilized catalyst showed excellent activity for various quinoxalines and other N-heteroarenes, and maintained high activity during recycling, making it suitable for continuous flow synthesis.
Review
Chemistry, Multidisciplinary
Nicolas Fantozzi, Jean-Noel Volle, Andrea Porcheddu, David Virieux, Felipe Garcia, Evelina Colacino
Summary: This article highlights the significance of green chemistry methods for promoting sustainable development, with a focus on batch and continuous mechanochemical methods in organic synthesis. The environmentally-friendly aspects of these methods are objectively assessed using green metrics and indicators, providing a comprehensive evaluation of their greenness. The article also provides an introduction to the topic, discusses variables influencing reaction outcomes, and offers an outlook for future research in this field.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Lucas Mele, Raphael El Bekri Saudain, Jean-Luc Pirat, David Virieux, Tahar Ayad
Summary: A simple and rapid microwave-assisted protocol for the selective alkaline hydrolysis of phosphonate diesters has been developed, allowing efficient access to a wide variety of diversely substituted phosphonic acid monoesters. Conventional approaches struggle to obtain such compounds.
Review
Chemistry, Physical
Hadi Salemi, Maarten Debruyne, Veronique Van Speybroeck, Pascal Van Der Voort, Matthias D'hooghe, Christian Stevens
Summary: Covalent organic frameworks (COFs) are newly emerging materials with high porosity and tuneable features. They have the potential to be a host for immobilizing metal catalysts, and their unique properties, such as high surface area, oriented channels, and heteroatom enrichment, make them promising for improving the disadvantages of heterogeneous metal catalysts.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
