Article
Chemistry, Multidisciplinary
Zhi-Xin Zhang, Li-Gao Liu, Yi-Xi Liu, Jian Lin, Xin Lu, Long-Wu Ye, Bo Zhou
Summary: Catalytic enantioselective transformation of alkynes is an important method for synthesizing axially chiral molecules. This study presents an organocatalytic approach for the atroposelective intramolecular (4 + 2) annulation of enals with ynamides. The method allows for the efficient and atom-economical preparation of various axially chiral 7-aryl indolines with good enantioselectivity. Computational studies were conducted to understand the regioselectivity and enantioselectivity, and a chiral phosphine ligand derived from the synthesized molecules showed potential for asymmetric catalysis.
Article
Chemistry, Multidisciplinary
Changwei Chen, Hongyu Zhang, Gang Xu, Sunliang Cui
Summary: This study demonstrates the oxoarylation of ynamides with N-aryl hydroxamic acids, and probes the mechanism and scalability through deuterium-labelling reaction and gram-scale reaction.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Applied
Rongxing Zhang, Zhijie Wu, Shaoqian Yang, Dawei Ma
Summary: An asymmetric approach to install substituted imidazo[1,2-a]-indol-3-ones was reported in this study, which relied on a Pd/diamidophosphite-catalyzed intramolecular dearomative allylic substitution of 1,3-disubstituted indoles derived from 3-formylindoles and amino acids. Enantioselective total syntheses of (-)-spiroquinazoline and three related alkaloids were successfully achieved.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Tzu-Lun Liu, Meng-Li Jhou, Cheng-En Hsieh, Chia-Jung Lin, Hsiu-Hui Su, Chih-Ming Chou
Summary: This study presents a protocol for the preparation of functionalized N-allyl-N-aryl sulfonamides via palladium-catalyzed intramolecular decarboxylative N-allylation reaction, showing good regioselectivity. Additionally, transformation of N-allyl-N-aryl sulfonamide into 4-aryl-1,2,3,4-tetrahydroquinoline and nitrogen-containing beta-hydroxysulfide bioactives has been demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Galla V. Karunakar, Chittala Emmaniel Raju, Karra Sai Bhavani Nagasri Himaja, Perla Bharath Kumar, Balasubramanian Sridhar
Summary: N-aryl-1H-pyrazolyl substituted benzenesulfonamide derivatives were regioselectively obtained from ynamides and pyrazoles through silver-catalyzed reaction. In this intermolecular organic transformation, several substituted benzenesulfonamides were obtained in good to excellent yields by forming a new C-N bond under mild reaction conditions.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Lan Zhao, Changfu Qiu, Lixin Zhao, Guangwei Yin, Fangyi Li, Chunhua Wang, Zheng Li
Summary: Described is an efficient method for the synthesis of 1H- and 3H-indoles, which does not require the use of transition metal or stoichiometric amount of oxidant. The process is operationally simple, easily scalable, and exhibits good substrate tolerability. Control experiments suggest the reactions may proceed in a tandem sequence of bromination and intramolecular Friedel-Crafts alkylation in a one-pot procedure.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Wei Li, Jie Qiu, Hengyuan Li, Wanli Chen, Cheng Hou, Huaifeng Li
Summary: By utilizing the radical reactivity of neutral diazoacetates, we have developed a method for synthesizing indole compounds, especially valuable [a]-annulated indoles, without the need for transition metals, oxidants, or substrate prefunctionalization. This visible-light-driven transformation is enabled by a single organophotocatalyst, without the use of metals or additives.
Article
Chemistry, Multidisciplinary
Joachim Loup, Egor M. Larin, Mark Lautens
Summary: A reductive cyclization using ortho-vinylanilides for preparing N-heterocycles was catalyzed by an inexpensive and bench-stable iron complex at ambient temperature. The reaction likely involves hydromagnesiation of the vinyl group and trapping of the generated benzylic anion by an intramolecular electrophile. This method showed broad applicability in synthesizing substituted indoles, oxindoles, and tetrahydrobenzoazepinoindolone derivatives, with mechanistic studies revealing the reversibility of the hydride transfer step. The synthetic utility was further demonstrated by the formal synthesis of a bioactive compound and a group of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Chen Su, Wen-Hua Xu, Rui-Li Guo, Xing-Long Zhang, Xue-Qing Zhu, Ya-Ru Gao, Yong-Qiang Wang
Summary: This study developed a novel method for the synthesis of aporphine analogues, utilizing an intramolecular dehydrogenative coupling of two inert aryl C-H bonds. The method not only exhibits high compatibility with various functional groups, but has also been further applied for the synthesis of natural products aporphine and zenkerine.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Jiann-Jyh Huang, Hung-Chun Liao, Cheng-En Hsu, Yan-Ru Liu, Yi-Fu Chang, Shan-Yen Chou
Summary: In this study, a method for synthesizing spirocyclopropane-containing 4H-pyrazolo[1,5-a]indoles was reported. The targets were obtained with high yields through alkylative dearomatization and intramolecular N-imination reactions.
Article
Chemistry, Organic
Capucine Mahe, Olivier Blacque, Gilles Gasser, Vincent Gandon, Kevin Cariou
Summary: The first synthesis of various N-metallocenyl ynamides has been achieved, along with the development of two strategies for the oxidative cyclization of N-ferrocenyl ynamide into ansa[3]-ferrocenylamide. The mechanism for the iodine(III)-triggered transformation has been investigated using DFT calculations, revealing a concerted iodination deprotonation step.
Article
Chemistry, Organic
Nicolas Brach, Lucas Popek, Mathieu Truong, Claire Laurent, Vincent Bizet, Krishna P. Kaliappan, Nicolas Blanchard
Summary: Pyrazines can undergo intramolecular cascade reactions at room temperature, leading to the formation of specific compounds. The study also revealed the significant influence of substituents on the distribution of reaction products.
Article
Chemistry, Organic
Genlai Zhou, Jingwen Su, Tianbo Shang, Xiaojuan Wang, Yihui Bai, Zheliang Yuan, Gangguo Zhu
Summary: A novel transformation of N-allyl ynamides was developed, enabling the synthesis of nitrogen-fused tricyclic compounds under mild reaction conditions through cascade reactions. This represents a rare example of 4-exo-dig radical cyclization, providing a new opportunity for the construction of synthetically appealing azetidines from readily available N-allyl ynamides.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
Zhaosheng Liu, Xiaochen Ji, Feng Zhao, Guojun Deng, Huawen Huang
Summary: A novel metal-free photoredox-catalyzed cyclization reaction of N-aryl acrylamide is presented, which produces valuable oxindole derivatives through the mediation of H2O and aldehyde. Sustainable visible light was employed as the energy source, and the organic light-emitting molecule 4CzIPN acted as the efficient photocatalyst. The main features of this reaction are environmentally-friendly conditions and high yields.
Article
Chemistry, Organic
Ya-Nan Ding, Yan-Chong Huang, Wei-Yu Shi, Nian Zheng, Cui-Tian Wang, Xi Chen, Yang An, Zhe Zhang, Yong-Min Liang
Summary: A novel palladium-catalyzed domino procedure has been described for the preparation of (hetero)aryl thio/selenoglycosides, utilizing readily available (hetero)aryl iodides and easily accessible 1-thiosugars/1-selenosugars as substrates. The method shows good regio- and stereoselectivity, high efficiency, and broad applicability for 10 types of sugars, with up to 89% yield and 53 examples.
Article
Chemistry, Multidisciplinary
Sovan Biswas, Ben F. Van Steijvoort, Marjo Waeterschoot, Narendraprasad Reddy Bheemireddy, Gwilherm Evano, Bert U. W. Maes
Summary: Bridged nitrogen bicyclic skeletons have been accessed via unprecedented site- and diastereoselective orthogonal tandem catalysis from readily accessible reactants in a step economic manner. The protocol allows for the preparation of substituted analogues with ease, and the use of a Cu catalyst in the Ullmann-Goldberg reaction helps avoid interference from off-cycle Pd catalyst scavenging.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Hajar Baguia, Gwilherm Evano
Summary: This study presents an efficient process for the copper-catalyzed direct perfluoroalkylation of C-H bonds in heteroarenes using commercially available perfluoroalkyl iodides. The combination of copper(I) iodide and 1,10-phenanthroline enables the easy reduction of perfluoroalkyl iodides to radical species that add to a wide range of heteroarenes, showcasing high regioselectivity. The efficiency and robustness of this process is demonstrated by the direct perfluoroalkylation of furan-containing peptides.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Multidisciplinary Sciences
Clement Jacob, Hajar Baguia, Amaury Dubart, Samuel Oger, Pierre Thilmany, Jerome Beaudelot, Christopher Deldaele, Stefano Perusko, Yohann Landrain, Bastien Michelet, Samuel Neale, Eugenie Romero, Cecile Moucheron, Veronique Van Speybroeck, Cedric Theunissen, Gwilherm Evano
Summary: This study reports a general anti-Baldwin radical 4-exo-dig cyclization from nitrogen-substituted alkynes. Under visible light irradiation in the presence of a heteroleptic copper complex and an amine, a range of ynamides smoothly cyclize to the corresponding azetidines. The cyclization reaction shows full control of the regioselectivity, allowing the synthesis of useful building blocks in natural product synthesis and medicinal chemistry.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Gilles De Smet, Xingfeng Bai, Carl Mensch, Sergey Sergeyev, Gwilherm Evano, Bert U. W. Maes
Summary: This study demonstrates that acetate can serve as a renewable leaving group for selective deoxygenation of phenolics. The Ni-catalyzed reaction in a green solvent allows for efficient deoxygenation without affecting specific functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Hajar Baguia, Gwilherm Evano
Summary: Perfluoroalkylated (hetero)arenes are a highly important family of molecules used in various fields such as medicinal chemistry, agrochemistry, and material sciences. There has been significant interest in their synthesis, particularly through direct perfluoroalkylation of C(sp(2))-H bonds in (hetero)arenes with high regioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Johanne Ling, Antoine Bruneau-Voisine, Guillaume Journot, Gwilherm Evano
Summary: In this study, a general copper-catalyzed carbonylative cross-coupling between amines and alkyl iodides was reported. The reaction showed good efficiency and broad substrate scope, making it potentially valuable for industrial applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Polymer Science
Fabiana Siragusa, Jeremy Demarteau, Thomas Habets, Ion Olazabal, Koen Robeyns, Gwilherm Evano, Raphael Mereau, Thierry Tassaing, Bruno Grignard, Haritz Sardon, Christophe Detrembleur
Summary: In this study, a new depolymerization method for step-growth polymers is reported, which can be degraded into their native precursor or added-value offspring, while generating hemiacetal cyclic carbonate. The specific functionalities in the polymer trigger degradation at a certain temperature and in the presence of an organic base catalyst, and can be fully degraded within 2 hours without the need for solution conditions.
Article
Chemistry, Organic
Chunyang Zhang, Nicolas Blanchard, Gwilherm Evano
Summary: An efficient radical cyclization of suitably functionalized ynamides to nitrogen-containing heterocycles is reported. The reaction shows high regio- and stereoselectivity, leading to good to excellent yields. Additionally, the exocyclic double bond can be used for further chemical diversification, and the generality of this radical cyclization is demonstrated by its extension to the synthesis of other nitrogen heterocycles.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Fabiana Siragusa, Thomas Habets, Raphael Mereau, Gwilherm Evano, Bruno Grignard, Christophe Detrembleur
Summary: Designing easily degradable polymers is crucial to reduce the accumulation of post-consumer plastic waste. In this study, regioregular polycarbonates prepared by organocatalyzed copolymerization were chemically recycled, providing a feasible method for the synthesis of novel degradable polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Review
Chemistry, Multidisciplinary
Jerome Beaudelot, Samuel Oger, Stefano Perusko, Tuan-Anh Phan, Titouan Teunens, Cecile Moucheron, Gwilherm Evano
Summary: Photocatalyzed and photosensitized chemical processes, particularly using photoactive copper(I) complexes, have gained significant attention and application in various fields. This review provides a comprehensive overview of the structural, photophysical, and electrochemical properties of mononuclear copper(I) complexes, highlighting critical structural parameters and their impact on the properties. It also explores the main areas of application for these complexes, such as photoredox catalysis, hydrogen production, photoreduction of carbon dioxide, and dye-sensitized solar cells.
Article
Chemistry, Organic
Omaima Adaoudi, Julie Le Bescont, Antoine Bruneau-Voisine, Gwilherm Evano
Summary: A general and inexpensive catalytic system for copper-catalyzed carbonylative coupling between alkyl iodides and alcohols or sodium hydroxide has been reported. Under mild pressure of carbon monoxide (5 bar) and catalytic amounts of copper(I) chloride and N,N,N',N?,N?-pentamethyldiethylenetriamine, a variety of secondary and tertiary alkyl iodides are easily converted into the corresponding esters and carboxylic acids without competing direct nucleophilic substitution. The main advantages of this procedure include broad applicability, the use of an especially inexpensive and available catalytic system, and user-friendliness.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Organic
Clement Jacob, Julien Annibaletto, Bert U. W. Maes, Gwilherm Evano
Summary: This review article presents and discusses the regioselectivity of the direct arylation reactions of anilines, focusing on the ortho, meta, and para positions. These reactions provide a straightforward method for the synthesis of arylated anilines without prefunctionalization. The factors influencing the reactivity and selectivity of these reactions are also emphasized.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Fabiana Siragusa, Thomas Habets, Raphael Mereau, Gwilherm Evano, Bruno Grignard, Christophe Detrembleur
Summary: This study presents a new type of degradable polymer that can be easily and completely degraded into its monomers under mild conditions through catalyst-free aminolysis. The recovered monomers can then be used for polymer synthesis, offering a closed-loop recycling scenario. This work is of great significance for addressing the accumulation of post-consumer plastic waste and providing building blocks for the synthesis of novel degradable polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Swetha Jos, Christine Tan, Pierre Thilmany, Alaa Saadane, Carla Slebodnick, Gwilherm Evano, Webster L. Santos
Summary: We have reported a tri-n-butyl phosphine catalyzed hydroboration reaction of ynamides, which provides regio- and stereo-selective formation of (Z)-beta-borylenamides in good yields. Surprisingly, a formal cis addition to the triple bond was observed, and this finding was confirmed by NMR and X-ray crystallography. P-31 NMR studies suggest that a zwitterionic vinylphosphonium intermediate plays a key role in the reaction mechanism. Furthermore, the resulting products were successfully transformed into beta-CF3 enamides via stereoretentive trifluoromethylation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hajar Baguia, Jerome Beaudelot, Cecile Moucheron, Gwilherm Evano
Summary: An efficient and general process for the direct perfluoroalkylation of C-H bonds in heteroarenes using copper catalysis has been reported. The reaction is photoinduced and operates at room temperature, making it a redox neutral process.
CHEMICAL COMMUNICATIONS
(2022)
