Article
Chemistry, Organic
Huan Xu, Xinyao Lou, Junrang Xie, Ze Qin, Huan He, Xiaofang Gao
Summary: A different regioselective three-component reaction of alkenes, oxygen sources, and hydroperoxides mediated by ammonium iodine to alpha-oxyperoxidates has been developed. Mechanistic studies showed that regioselective radical addition and subsequent S(N)2 nucleophilic substitution can lead to the formation of products. In addition to the traditional pathway of S(N)2 reaction, an unusual transition configuration involving H2O attacking the alpha-C atom at the front side was also observed.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Na Chen, Ting-Ting Deng, Jin-Quan Li, Xin-Yue Cui, Wen-Wu Sun, Bin Wu
Summary: In this study, we report a hypervalent iodine-mediated umpolung strategy for the dialkoxylation of N-substituted indoles, resulting in the formation of trans-2,3-dimethoxyindolines with up to 95% yield. We also achieved C5-selective bromination of 2,3-dialkoxyindoline via NBS-mediated rearomatization. Additionally, DFT calculation was used to study the sequence of electrophilic addition and nucleophilic substitution pathway of N-substituted indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Qing-Qing Han, De-Mao Chen, Zu-Li Wang, Yuan-Yuan Sun, Shao-Hui Yang, Jing-Cheng Song, Dao-Qing Dong
Summary: An efficient and facile method for C-H amination of quinoxalinones with heteroaromatic amines under metal-free conditions has been described. The desired products with various groups were obtained with moderate to high yields in the presence of hypervalent PIDA reagent.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Organic
Yumiko Suzuki, Ren Takehara, Kasumi Miura, Ryota Ito, Noriyuki Suzuki
Summary: A facile and regioselective synthesis of trisubstituted quinoxalines was developed using hypervalent iodine reagents as catalysts. Excellent regioselectivities were achieved in the annulation reaction between alpha-iminoethanones and o-phenylenediamines, demonstrating potential utility in medicinal chemistry and materials sciences.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Fangling Lu, Kan Zhang, Yanxiu Yao, Ying Yin, Jiafu Chen, Xinwei Zhang, Yin Wang, Lijun Lu, Ziwei Gao, Aiwen Lei
Summary: A highly stereoselective synthesis of thiocyanated enaminones was achieved through an electrochemical process, with up to 87% yields. The transformation proceeded smoothly without the need for external oxidants, electrolytes, or transition-metal catalysts, showcasing its potential for practical application.
Article
Chemistry, Organic
Grace A. Lutovsky, Ellie F. Plachinski, Nicholas L. Reed, Tehshik P. Yoon
Summary: A method for allylic amination using photoredox activation and Cu(II)-mediated radical-polar crossover is described. This strategy allows the synthesis of a range of structurally varied allylic amines. The regioselectivity of this process complements that of conventional methods for allylic amination.
Article
Chemistry, Organic
Liang Zhang, Neng-Jie Mou, Dong-Rong Xiao, Xin Zhuang, Xiao-Long Lin, Tian Cai, Qun-Li Luo
Summary: Functionalized oxa-heterocycles, basic structural units in natural products and bioactive molecules, can be efficiently synthesized through iodine-mediated annulation of propargylic alcohols with cyclic 1,3-dicarbonyl compounds, leading to novel cyclic scaffolds with high regioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Mitsumi Takeda, Saki Maejima, Eiji Yamaguchi, Akichika Itoh
Summary: This study presents a versatile methodology for the synthesis of alpha-aminocarbonyl compounds via direct CAN bond formation by reacting dimethyl methylmalonate with various amines in the presence of molecular iodine. The strategy involves in situ iodination of the dimethyl methylmalonate, promoting its enolate isomer formation for nucleophilic substitution with an amine. The practical approach is industry-friendly as it uses readily available reagents without the need for pre-preparation of amines and other substrates.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Applied
Stanislav A. Paveliev, Oleg O. Segida, Oleg Bityukov, Hai-Tao Tang, Ying-Ming Pan, Gennady Nikishin, Alexander O. Terent'ev
Summary: In this study, the electrochemical intramolecular cross-dehydrogenative C(sp(2))-H/N-H coupling of alpha,beta-unsaturated hydrazones resulting in substituted pyrazoles has been discovered. This process is catalyzed by hypervalent iodine species generated in situ through anodic oxidation of aryl iodide in fluorinated alcohol media. The formation of hypervalent iodine compound and its key role in the construction of a new C-N bond were confirmed with CV and NMR experiments. A wide range of substituted pyrazoles were obtained with yields ranging from 46% to 88%.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Ya-Nan Li, Fan Chen, Xing-Guo Zhang, Hai-Yong Tu
Summary: An iodine-mediated radical cyclization reaction of o-vinylaryl isocyanides with disulfides or diselenides has been developed, providing an atom-economic method for the regioselective construction of 2-chalcogenated quinolines with high yields by incorporating both chalcogen atoms of the disulfides or diselenides.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Yingying Zhang, Yating Huang, Kewei Yu, Xiaoxiang Zhang, Wenhua Yu, Jiale Tang, Yiran Tian, Wanxing Wei, Zhuan Zhang, Taoyuan Liang
Summary: Herein, we report a novel iron and iodine cooperative catalytic system for the synthesis of diverse 2-amino-3-alkylindoles. The method exhibits good substrate and functional group compatibility, and the catalyst system and feedstocks are readily available, showing great potential for further exploration of biological activities.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Yuanbo Li, Fan Chen, Shengqing Zhu, Lingling Chu
Summary: This study presents a metal-free photoinduced triiodide-mediated [3 + 2] cycloaddition of N-Ts aziridines with alkenes, utilizing a simple protocol and TBAI as a radical mediator to achieve regioselective access to substituted pyrrolidines with good functional group compatibility. Preliminary mechanistic experiments suggested that TBAI(3) generated in situ from TBAI played a crucial role in promoting the radical ring-opening of N-Ts aziridines.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Song Cheng, Wen Gu, Kun Zhao, Shu Ting Zhang, Lan Yang, Qing Song Liu, Xiao Xiao Li, Zhi Gang Zhao
Summary: A strategy for synthesizing iodo-substituted allylic pyrazoles through NIS-mediated regioselective addition is presented. This reaction is fast, scalable, and tolerant of a wide range of substrates. Additionally, the products can undergo coupling reactions with phenylacetylene under Sonogashira cross-coupling conditions.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Xinyi Wan, Haiwen Li, Shan Wang, Cunde Wang
Summary: A method mediated by acetic acid was developed for the synthesis of highly stereoselective tetrahydrothiopyranols. The method is characterized by cheap and readily available starting materials, simple operation, and mild reaction conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ying Lin, Dongyang Li, Jingjing Zhang, Zhi Tang, Long Liu, Tianzeng Huang, Chunya Li, Tieqiao Chen
Summary: The protocol efficiently synthesizes N-aryl-substituted azacycles using aryl amines and cyclic ethers with I-2/NaH2PO2, yielding products with good functional group tolerance. The reaction can be easily scaled up to produce gram-scale amounts and further chemical modifications of the products enable useful transformations of the quinoline ring, including bromination and acetylation.
NEW JOURNAL OF CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Xiao Tang, Songtao Ding, Liangliang Song, Erik V. V. Van der Eycken
Summary: The isoindolo[2,1-b]isoquinolin-5(7H)-one scaffold is a widely found core structure in many bioactive natural products. Transition metal-catalyzed C-H activation/annulation has emerged as a powerful method to construct diverse polyheterocycles and has been employed for the synthesis of isoindolo[2,1-b]isoquinolin-5(7H)-one. This review provides an overview of recent advances in the preparation of isoindolo[2,1-b]isoquinolin-5(7H)-ones using transition metal-catalyzed C-H activation/annulation, aiming to help researchers discover hidden opportunities and accelerate the discovery of novel transformations based on C-H activation/annulation.
Article
Chemistry, Organic
Javier E. Alfonso-Ramos, Ruben Van Lommel, David Hernandez-Castillo, Frank De Proft, Roy Gonzalez-Aleman, Erik V. Van der Eycken, Gerardo M. Ojeda-Carralero
Summary: 3-Dipolar cycloadditions are commonly used to form five-membered heterocycles, but the cycloadditions involving acyl-isocyanide ylides have not been well explored by the chemical community. In this study, we investigated the mechanistic features of the reaction between acyl-isocyanide ylides and dipolarophiles using density functional theory calculations. We explained the experimental results and predicted opposite regioselectivity for electron-poor and electron-rich dipolarophiles. This study provides insights for the design of new cycloaddition reactions based on the acyl-isocyanide ylides motif.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Health Care Sciences & Services
Christiaan Vis, Josien Schuurmans, Bruno Aouizerate, Mette Atipei Craggs, Philip Batterham, Leah Buhrmann, Alison Calear, Arlinda Cerga Pashoja, Helen Christensen, Els Dozeman, Claus Duedal Pedersen, David Daniel Ebert, Anne Etzelmueller, Naim Fanaj, Tracy L. Finch, Denise Hanssen, Ulrich Hegerl, Adriaan Hoogendoorn, Kim Mathiasen, Carl May, Andia Meksi, Sevim Mustafa, Bridianne O'Dea, Caroline Oehler, Jordi Piera-Jimenez, Sebastian Potthoff, Gentiana Qirjako, Tim Rapley, Judith Rosmalen, Ylenia Sacco, Ludovic Samalin, Mette Maria Skjoth, Kristine Tarp, Ingrid Titzler, Erik Van der Eycken, Claire Rosalie van Genugten, Alexis Whitton, Enrico Zanalda, Jan H. Smit, Heleen Riper
Summary: This study compared the effectiveness of the ItFits-toolkit with implementation-as-usual in implementing iCBT services in routine mental health care organizations. The ItFits-toolkit performed better in supporting implementers in developing and applying effective tailored implementation strategies, but had a small effect on normalization levels among service providers.
JOURNAL OF MEDICAL INTERNET RESEARCH
(2023)
Review
Chemistry, Multidisciplinary
Xiao Tang, Liangliang Song, Erik V. Van Der Eycken
Summary: The Ugi reaction is highly explored due to its mild reaction conditions, wide scope, and high variability for the formation of multifunctional adducts. By carefully selecting the starting four components, Ugi-adducts can undergo different post-transformations to synthesize bioactive heterocycles, natural products, and macrocycles. Various post-Ugi transformations have been developed for constructing structurally novel polycycles, and this account summarizes important efforts for the synthesis of polycyclic N-heterocycles via post-Ugi cyclizations from the Van der Eycken laboratory onwards 2016. With the aid of transition metal catalysis and metal-free strategies, versatile polyheterocycles are prepared with high efficiency and step-economy.
Review
Chemistry, Multidisciplinary
Xianjun Xu, Ling Zhong, Huangdi Feng, Erik V. V. Van Der Eycken
Summary: The metal-free dearomatization reactions have proven to be a green and sustainable method for constructing spirocyclic, polycyclic, and heterocyclic scaffolds. This review focuses on recent advances in metal-free dearomatization reactions, including organo-catalyzed, oxidative, Bronsted acid- or base-promoted, photoredox-catalyzed, and electrochemical oxidation dearomatization reactions.
Article
Chemistry, Multidisciplinary
Laura Y. Vazquez-Amaya, Guglielmo A. Coppola, Erik V. Van der Eycken, Upendra K. Sharma
Summary: The popularity of microflow chemistry has significantly increased in the last 20 years, leading to a transition from macro-batch reactors to miniaturized flow devices among chemists. Microfluidics has established itself as not just a trend but a new, effective, and sustainable way of conducting chemistry in the field of organic chemistry, with continuous growth and evolution expected. This perspective highlights the use of innovative enhancing technologies applied to microflow reactors, as well as examples of complex integrated microsystems and scale-up technologies, showcasing microflow as a promising choice for the future.
Article
Chemistry, Organic
Liangliang Song, Zhenwei Lv, Yan Li, Kui Zhang, Erik V. Van der Eycken, Lingchao Cai
Summary: In this study, a Rh(III)-catalyzed C-H activation/annulation reaction was developed for the diversification of Lys-based peptides, yielding a range of peptide-isoquinolone conjugates. This method offers racemization-free conditions, high atom and step economy, excellent chemo- and site-selectivity, and broad substrate scope. Furthermore, the peptide-isoquinolone conjugates demonstrate good fluorescent properties and show potential antifungal activity against crop and forest pathogenic fungi, with a particular conjugate exhibiting superior activity compared to the positive control.
Article
Chemistry, Organic
Laura Y. Y. Vazquez-Amaya, Brecht Dootselaere, Gerardo M. M. Ojeda-Carralero, Serena Pillitteri, Johan Van der Eycken, Erik V. V. Van der Eycken, Upendra K. K. Sharma
Summary: Here, we report a one-pot aminoalkylation reaction of styrene derivatives with boronic acids and boronic acid pinacol esters. This reaction provides a mild and easily accessible method for the synthesis of complex secondary amines in moderate to high yields. Additionally, we demonstrate the activation of alkyl boronic acid derivatives by imines in a photoredox process for the first time, which serves as both substrate and Lewis base activator in the reaction. The applicability of this protocol is greatly enhanced by its successful adaptation to photoflow reactors.
Article
Chemistry, Organic
Monica Oliva, Viktoriia V. Chernobrovkina, Erik V. van der Eycken, Upendra Kumar Sharma
Summary: Photoredox catalysis has gained significant attention in the synthetic community due to its ability to form challenging C-C and C-heteroatom bonds under mild and sustainable conditions. Developing novel synthetic strategies and suitable technologies to overcome scale-up issues has become a primary focus. Continuous-flow reactors play a major role in increasing the efficiency and accessibility of photocatalyzed reactions. Recent interest in using boron species as radical precursors in photocatalyzed reactions has emerged, despite the challenges posed by the high oxidation potential of boronic acids. This Account highlights recent contributions to this field with a focus on applicability, selectivity, and scalability through continuous-flow methodology.
Article
Chemistry, Multidisciplinary
Chao Liu, Johan Van Der Eycken, Erik V. Van Der Eycken
Summary: A novel method was developed for transition metal-free N-S bond cleavage and subsequent C-N bond activation of Ugi-adducts. Diverse primary amides and a-ketoamides were prepared in a rapid, step-economic, and highly efficient manner in two steps. This strategy offers excellent chemoselectivity, high yield, and functional-group tolerance. Primary amides derived from the pharmaceuticals probenecid and febuxostat were successfully prepared. This method provides a new environmentally friendly pathway for the simultaneous synthesis of primary amides and a-ketoamides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Arina Y. Obydennik, Alexander A. Titov, Anna V. Listratova, Tatiana N. Borisova, Irina L. Sokolova, Victor B. Rybakov, Erik V. Van der Eycken, Leonid G. Voskressensky, Alexey V. Varlamov
Summary: In this study, 1-substituted 1-ethynyl-2-vinyldi- and tetrahydroisoquinolines were successfully subjected to [3,3]-sigmatropic rearrangement under microwave irradiation at 150 degrees Celsius in toluene, in the presence of nucleophiles (DMAP, triphenylphosphine and tetrahydrothiophene), yielding pyrrolo[2,1-b][3]benzazepines with good yields. The replacement of toluene with acetonitrile directed the rearrangement towards the formation of 7,11b-dihydro-6H-pyrido[2,1-a]isoquinolines.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Organic
Alisa A. Nevskaya, Anna D. Zinoveva, Erik V. van der Eycken, Leonid G. Voskressensky
Summary: This paper provides a review on the synthesis methodologies and applications of different indolizine derivatives, including thienoindolizines and indolizino[8,7-b]indoles. Indolizine nucleus is a privileged scaffold of various natural and synthetic molecules with significant biological activity. Fused-indolizines, such as thienoindolizines and indolizinoindoles, have attracted great interest due to their antitumor, antimicrobial, and enzyme inhibitor activity. The study summarizes the approaches to the synthesis, properties, and application of various indolizine derivatives, with a focus on recent articles on indolizines and indolizino[8,7-b]indoles, as well as a general review on thienoindolizine derivatives.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Liangliang Song, Lingchao Cai, Lei Gong, Erik V. Van der Eycken
Summary: Copper-catalyzed enantioselective coupling reactions have been extensively studied for the rapid synthesis of chiral molecules. Despite progress in polar and radical mechanisms, the development of general and practical strategies for the regio-, enantio-, and diastereoselective assembly of stereogenic centers remains challenging. The integration of photocatalysis with asymmetric copper catalysis offers new reaction pathways and diverse chiral compounds, expanding the scope of radical chemistry. This review provides a summary of recent advances in photoinduced copper-catalyzed enantioselective coupling reactions, with a discussion on the mechanistic aspects.
CHEMICAL SOCIETY REVIEWS
(2023)
Review
Chemistry, Multidisciplinary
Alexey A. Festa, Olga A. Storozhenko, Leonid G. Voskressensky, Erik V. van der Eycken
Summary: The use of visible light-promoted chemistry in halogenation and halofunctionalisation reactions has significant impact.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Chao Liu, Liangliang Song, Vsevolod A. Peshkov, Erik V. Van der Eycken
Summary: A transition metal-free method for C-S bond cleavage and Mannich reaction of Ugi-adducts with alcohols and thiols has been developed, leading to the synthesis of diverse novel peptidomimetics containing N,O- or N,S-aminals. This method exhibits exclusive selectivity, broad substrate scope, excellent yield, and tolerance towards different functional groups, and has been successfully applied to substrates derived from pharmaceuticals febuxostat, probenecid, and memantine.