Article
Chemistry, Organic
Su Hyeon Park, Sunwoo Lee
Summary: The selective synthesis of (Z)- and (E)-beta-fluoro-alpha,beta-unsaturated amides is achieved through the aminocarbonylation reaction. The choice of catalyst and reaction conditions determines the formation of (Z)- or (E)-isomers. The substituents on the phenyl ring of the vinylarenes can be varied, resulting in controlled yields and selectivity.
Article
Chemistry, Organic
Su Hyeon Park, Sunwoo Lee
Summary: In this study, the selective synthesis of (Z)- and (E)-ss-fluoro-alpha, ss-unsaturated amides via palladium-catalyzed aminocarbonylation of 1-fluoro-2,2-diiodovinylarenes is described. The choice of catalyst and base, as well as the substitution on the phenyl ring, have a significant impact on the selectivity and yield of the products.
Article
Chemistry, Organic
Marine Pinaud, Eric Huet, Marc Presset, Erwan Le Gall
Summary: A straightforward and modular method for the synthesis of substituted spirocyclic tetrahydrofurans is described. The strategy involves a reductive cobalt-catalyzed three-component reaction and an intramolecular iodoetherification reaction, allowing for the preparation of diverse spirocyclic compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Dequan Zhang, Jialin Wen, Xumu Zhang
Summary: The construction of chiral quaternary carbon stereocenters has been a long-standing challenge in organic chemistry. In this study, a hydroformylation approach was reported to access chiral quaternary stereogenic centers, and a variety of chiral alpha-quaternary amino acids could be synthesized. The regioselectivity was found to be influenced by the electronic properties of the substituents, and a substrate-catalyst interaction model was proposed based on the chiral environment of the rhodium/Yanphos complex.
Article
Chemistry, Organic
Christian Wulkesch, Constantin Czekelius
Summary: The study highlights a mild, operationally simple, and inexpensive photocatalytic perfluoroalkenylation reaction for the direct synthesis of tetrasubstituted, highly electron-deficient enals from aldehydes. The one-step reaction is tolerant to various functional groups and can be applied to a wide range of substrates, with product yields ranging from 52-84%.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Francesco Fini, Alessandro Zanni, Maria Luisa Introvigne, Mattia Stucchi, Emilia Caselli, Fabio Prati
Summary: This study presents a straightforward concise synthesis of chiral non-racemic aliphatic alpha-boryl isocyanides, which serve as relay intermediates for boron-based bioactive molecules in multicomponent reactions. The short synthetic sequence includes key steps such as copper-catalysed asymmetric borylation of imines, simultaneous nitrogen formylation/boron-protecting group interconversion, and the final formamide dehydration reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Ronja Priester, Uli Kazmaier
Summary: The Matteson homologation is an efficient method for synthesizing polyketide-peptide natural products, such as emericellamides. It allows for the quick and selective synthesis of a polyketide fragment with three stereogenic centers, in only four steps. The peptide fragment can be easily obtained through solid-phase peptide synthesis.
Review
Chemistry, Organic
Laurence Feray, Michele P. Bertrand, Aurelien Galibert-Guijarro
Summary: This Short Review provides an updated overview of the synthesis of alpha-haloenamides, which are a versatile subclass of enamides. Alpha-haloenamides can be prepared from ynamides, acetamides, or gem-dibromoalkenes in the presence of N-nucleophiles and can be easily converted into more complex structures through halogenmetal exchange and transition-metal-catalyzed cross-coupling reactions.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Hui Yang, Jie Wang, Can Jin, Xiaoqing Li, Xiangsheng Xu
Summary: Selective hydrofluorination of alkynes using aqueous HF was achieved using a gold catalyst and an amide directing group. The fluorination occurred at the position distal to the amino group for both aryl- and alkyl-substituted propargylamines.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jeymy T. Sarmiento, Maria Carcel, Carmen Ramirez de Arellano, Teresa Varea, Gregorio Asensio, Andrea Olmos
Summary: In this study, alpha-chloromethylketimines have been synthesized through a gold-catalyzed hydroamination reaction of aromatic and aliphatic 1-chloroalkynes with aromatic amines. This method allows the preparation and spectroscopic characterization of alpha-chloromethylketimines with high purity, complete conversion, and atom economy. The synthetic usefulness of this methodology has been demonstrated through the preparation of beta-chloroamines and indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jun Wei, Jian Zhang, Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: A new method for the synthesis of chiral beta-amino amides using ambiphilic ynamides as two-carbon synthons has been established. The method allows for the efficient preparation of beta-amino amides with excellent chemo- and stereo-control, and has been successfully applied to the synthesis of over 100 desired products.
Article
Chemistry, Organic
Wenjuan Zhu, Hui Xi, Wenyang Jiao, Lihua Huang, Lianjie Wang, Junliang Wu
Summary: A visible-light-promoted alkoxysulfonylation of gem-difluoroalkenes using sulfonyl chlorides and alcohols has been developed. The reaction shows a broad substrate scope and excellent functional group compatibility. This method involves an atom transfer radical addition-like process, and the products can serve as platform molecules for further modification.
Article
Chemistry, Organic
Asaki Miyairi, Yoshihiro Oonishi, Yoshihiro Sato
Summary: This study successfully demonstrated the one-pot synthesis of fully substituted 2-aminofurans via a gold-catalyzed cascade reaction, under highly mild conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Atsushi Ueda, Yui Makura, Sana Kakazu, Takuma Kato, Tomohiro Umeno, Kazuhiro Hirayama, Mitsunobu Doi, Makoto Oba, Masakazu Tanaka
Summary: In this study, a selective E-type ring-closing metathesis reaction was discovered in α-helical stapled peptides. By using chiral carbocyclic α,α-disubstituted α-amino acids, a high E-selectivity was achieved, while standard acyclic amino acids resulted in lower selectivity. The stapled octapeptide exhibited a right-handed α-helical crystal structure.
Article
Chemistry, Organic
Huan He, Yanmei Wu, Yao Huang, Xue Li, Rui Wang, Jin-Song Yang, Xiao-Yu Liu, Yong Qin
Summary: A stereoselective glycosylation approach using a 4,6-O-tetraisopropyldisiloxanylidene-containing thio-fructofuranoside donor is described for alpha-D-fructofuranosides. This method exhibits broad substrate scope and good functional-group tolerance, enabling the efficient synthesis of the alpha-isomers of inulin oligosaccharides.
ORGANIC CHEMISTRY FRONTIERS
(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
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, Multidisciplinary
Bastien Michelet, Agnes Martin-Mingot, Jean Rodriguez, Sebastien Thibaudeau, Damien Bonne
Summary: Since the pioneer reports of the groups of Akiyama and Terada, the field of Bronsted acid organocatalysis has been continuously growing with the development of ingenious strategies for the activation of challenging substrates. Different approaches such as superacidic organocatalysts and the combination of Lewis and Bronsted acids have emerged, highlighting the complementarity of these strategies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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
Anthony J. Fernandes, Bastien Michelet, Armen Panossian, Agnes Martin-Mingot, Frederic R. Leroux, Sebastien Thibaudeau
Summary: Understanding the impact of emerging fluorinated motifs is crucial due to the increasing use of fluorine in various fields. This study demonstrates the significant effect of a local partial charge inversion through the replacement of a CHCH3 group with a CFCF3 group. This strategy enables the diastereoselective reduction of 5-membered ring oxocarbenium ions, leading to the formation of highly substituted tetrahydrofurans.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Maxime Artault, Thomas Cantin, Melissa Longuet, Kassandra Vitse, Christ Daniel Matatu Mbengo, Frederic Guegan, Bastien Michelet, Agnes Martin-Mingot, Sebastien Thibaudeau
Summary: This study reports a method to reorganize the core structure of aliphatic unsaturated nitrogen-containing substrates by exploiting polyprotonation in superacid solutions. The superelectrophilic activation of N-isopropyl systems allows for the selective functionalization of nitrogen-containing substrates. It is demonstrated that this skeletal reorganization can be controlled through protonation interplay.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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
Aline Delamare, Guillaume Naulet, Brice Kauffmann, Gilles Guichard, Guillaume Compain
Summary: The hexafluoroisobutyl group is a commonly found hydrophobic group in drugs, and its introduction can provide new advantages to compounds. However, the lack of a general and practical synthetic methodology has hindered the exploration of this modification. In this study, the first general method for introducing the hexafluoroisobutyl group into various compounds was reported. This method overcomes the usual fluoride beta-elimination observed with other CF3-vinyl groups, and it has been successfully applied to the multigram-scale synthesis of enantiopure (S)-5,5,5,5',5',5'-hexafluoroleucine.
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)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
