Article
Chemistry, Applied
Yu-ki Sugiyama, Masaki Amo, Kouta Ibe, Sentaro Okamoto
Summary: The reactivity of nitriles in a CoCl2-6H(2)O/dppe/Zn-catalyzed diyne-nitrile cycloaddition was studied. It was found that cyanamides are good substrates and result in the formation of 2-aminopyridines. Notably, N-unsubstituted cyanamide (H2N-CN) can react with 1,6-diynes to produce N-unsubstituted 2-aminopyridines, which cannot be obtained through other catalytic reactions and serve as versatile intermediates for further transformations.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Steve Huvelle, Pascal Matton, Christine Tran, Marie-Noelle Rager, Mansour Haddad, Virginie Ratovelomanana-Vidal
Summary: A convenient method for the ruthenium-catalyzed synthesis of benzo[c]naphthyridinone derivatives has been reported. The method shows high yields and regioselectivity, and is applicable to a wide range of substrates.
Article
Chemistry, Organic
Chuan-Chuan Wang, Ya-Li Qu, Xue-Hua Liu, Zhi-Wei Ma, Bo Yang, Zhi-Jing Liu, Xiao-Pei Chen, Ya-Jing Chen
Summary: In this study, the convenient preparation of N2-unprotected five-membered cyclic guanidines was achieved via a cascade [3 + 2] cycloaddition between organo-cyanamides and alpha-haloamides under mild conditions in good to excellent yields (up to 99%). The resulting cyclic guanidines could be easily transformed into hydantoins through hydrolysis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jian-Shu Wang, Qi Wang, Yiwen Zhu, Qian Gao, Jun Ying, Xiao-Feng Wu
Summary: A cobalt-catalyzed domino Pauson-Khand and [4 + 2] cycloaddition of substituted diynes has been developed for the rapid construction of complexed polycyclic ring systems. The reaction proceeded well using benzene-1,3,5-triyl triformate (TFBen) as the CO source, yielding various tetracyclic compounds with high yields, excellent regioselectivity, and diastereoselectivity. Control experiments were conducted to gain a better understanding of the reaction mechanism.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Nikolay Shcherbakov, Elena Chikunova, Dmitry Dar'in, Vadim Yu Kukushkin, Alexey Yu Dubovtsev
Summary: The Gold(I)-catalyzed [4 + 2] cycloaddition of indolylynamides and cyanamides is an efficient method for the synthesis of diversely substituted 1,3-diamino-beta-carbolines. This protocol is mild and tolerant to functional groups, allowing for successive functionalizations. Control experiments reveal the importance of reactant nature and catalyst identity in this developed cycloaddition.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
JingWen Jia, Yoshiko Yamaguchi, Tatsuya Ueda, Hiroko Yamada, Kiyomi Kakiuchi, Tsumoru Morimoto
Summary: We report the use of anthracene alpha-diketone as a CO source in carbonylation reactions. The high yield of cyclopentadienone was achieved through photoirradiation of a diyne in the presence of anthracene alpha-diketone and a rhodium(I) catalyst. This is the first demonstration of a CO-gas-free carbonylation reaction using anthracene alpha-diketone.
Article
Chemistry, Applied
Tatsuya Kumon, Shigeyuki Yamada, Tomohiro Agou, Hiroki Fukumoto, Toshio Kubota, Gerald B. Hammond, Tsutomu Konno
Summary: A regioselective cobalt-catalyzed [2+2+2] cycloaddition using fluorine-containing diynes with nitriles was successfully achieved, leading to the synthesis of α-fluoroalkylated pyridines in excellent yields. The reaction was conducted smoothly at 80 degrees C for 3 h using CoCl2(phen), zinc bromide, and zinc dust in dichloroethane. Additionally, dinitriles were also found to be suitable substrates for this reaction, yielding fluoroalkylated bipyridine derivatives in excellent yields.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Zhi-Yuan Chen, Meng-Wei Yang, Zi-Lu Wang, Yun-He Xu
Summary: In this research, a copper-catalyzed desymmetric protosilylation of prochiral diynes was developed, leading to the formation of products with moderate to high yields and enantiomeric ratios. This method provides a straightforward approach for synthesizing functionalized chiral tertiary alcohols in the presence of a chiral pyridine-bisimidazoline (Pybim) ligand.
Article
Chemistry, Organic
William Parisot, Steve Huvelle, Mansour Haddad, Guillaume Lefevre, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: Valuable 5H-chromeno[3,4-c]pyridines were conveniently synthesized through ruthenium-catalyzed [2 + 2 + 2] cycloaddition of diversely substituted alpha,omega-diynes with various cyanamides. The reaction exhibited high regioselectivity and tolerance towards a wide range of 1-ethynyl-2-(prop-2-yn-1-yloxy)benzene derivatives and cyanamides, providing 32 new tricyclic pyridines. These compounds can serve as building blocks for further functionalization and enable access to a biologically relevant intermediate.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Jian-Shu Wang, Jun Ying, Xiao-Feng Wu
Summary: A cobalt-catalyzed regioselective cycloaddition of unsymmetric diynes and nitriles has been developed for the synthesis of substituted pyridines. The reaction proceeds well using Co(OAc)(2)/bpy/Zn/ZnI2 as the catalytic system, giving various substituted pyridines with excellent yields and regioselectivities.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Organic
Vladimir A. Motornov, Andrey A. Tabolin, Yulia V. Nelyubina, Valentine G. Nenajdenko, Sema L. Ioffe
Summary: A new efficient method for the synthesis of multifunctionalized pyrrolidines via copper-catalyzed diastereoselective [3 + 2]-cycloaddition was developed, leading to the formation of novel fluorinated heterocycles like beta-fluoro-beta-nitropyrrolidines. The products exhibited good to excellent yields and high diastereoselectivity, and subsequent transformations resulted in the synthesis of medicinally attractive beta-fluoro-NH-pyrroles and other derivatives.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Sheba Ann Babu, P. V. Varsha, Susanna Poulose, Sunil Varughese, Jubi John
Summary: We have developed a direct method for the synthesis of polycyclic imidazo[1,2-a]pyridines via a copper-catalyzed annulation reaction. By using 3-nitroindoles and 2-aminopyridine, tetracenes, namely indole-fused imidazo[1,2-a]pyridines, can be synthesized. Pentacenes, namely indolo-imidazo[1,2-a]quinolines, can be generated from 2-aminoquinoline. Furthermore, benzothieno-imidazo[1,2-a]pyridines can be synthesized starting from 3-nitrobenzothiophene. The photophysical properties of these synthesized heteroacenes were also evaluated.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jin Zhou, Chen Chen, Qiwen Pang, Wei-Fang Zuo, Xiang Li, Gu Zhan, Qian-Qian Yang, Bo Han
Summary: A series of multifunctional dihydroquinolinone frameworks were synthesized through synergistic catalysis combining photolysis and Lewis base catalysis utilizing in situ generated ketenes from the visible-light-mediated Wolff rearrangement of alpha-diazoketones and ortho-amino MBH carbonates. This powerful [4 + 2] annulation further expands the application of MBH carbonates in cooperative catalysis and shows good compatibility and high efficiency. Furthermore, control experiments indicate that synergistic catalysis strategy plays a crucial role in the cycloaddition reaction, and a plausible mechanism is proposed to explain the reaction process.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Shuang Yang, Hai-Qing Wang, Jun-Nan Gao, Wen-Xin Tan, Yu-Chen Zhang, Feng Shi
Summary: A Lewis acid-catalyzed (3+2) cycloaddition of 2-indolylmethanols with beta,gamma-unsaturated alpha-ketoesters has been developed, leading to the synthesis of a series of cyclopenta[b]indoles with high yields and excellent diastereoselectivities. This reaction represents the first C3-nucleophilic (3+2) cycloaddition of 2-indolylmethanols and provides a good example for (2+n) cycloaddition of beta,gamma-unsaturated alpha-ketoesters, enriching the chemistry of 2-indolylmethanols. Additionally, this method offers an atom-economic and useful approach for constructing biologically important cyclopenta[b]indole scaffolds.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xin-Qi Zhu, Pan Hong, Yan-Xin Zheng, Ying-Ying Zhen, Feng-Lin Hong, Xin Lu, Long-Wu Ye
Summary: This study presents a copper-catalyzed asymmetric cyclization of alkenyl diynes involving a vinylic C(sp(2))-H functionalization, marking the first asymmetric vinylic C(sp(2))-H functionalization through cyclopentannulation. A revised mechanism involving a novel type of endocyclic copper carbene via remote-stereocontrol is proposed based on extensive mechanistic studies, providing new mechanistic insights into copper-catalyzed asymmetric diyne cyclization.
Article
Chemistry, Physical
Vincent Davenel, Chloe Puteaux, Christian Nisole, Fabien Fontaine-Vive, Jean-Marie Fourquez, Veronique Michelet
Summary: Efficient routes to access functionalized bicyclo[3.2.1]oct-2-ene and bicyclo[3.3.1]nonadiene via indium-mediated cycloisomerization of 1,6-enynes have been developed. The optimization of an atom-economical catalytic process using InCl3 led to high yields of up to 99% for the preparation of functionalized bicyclic adducts. The choice between 5-exo and 6-endo pathways in the cyclization reaction was influenced by the substitution of the alkynyl moiety, with electron-withdrawing groups favoring the exo isomer.
Article
Chemistry, Inorganic & Nuclear
Idir Benaissa, Katarzyna Gajda, Laure Vendier, Noel Lugan, Anna Kajetanowicz, Karol Grela, Veronique Michelet, Vincent Cesar, Stephanie Bastin
Summary: The coordination chemistry of anionic NHC based on an IPy platform substituted at the CS position was studied with transition-metal centers, showing different coordination modes and reaction mechanisms. A gold(I) intermediate was also discovered during the process and structurally characterized. These complexes exhibited high activities and a large tolerance towards functional groups in the synthesis of carboxylic acid derivatives.
Article
Chemistry, Organic
Romain Laher, Emilie Gentilini, Christophe Marin, Veronique Michelet
Summary: The study focuses on the synthesis of original structures with bicyclic scaffolds for the fragrance industry and evaluates their potential organoleptic properties. NHC-gold-type catalysts show excellent activities in the synthesis of various bicyclic adducts. The research also compares the similarities and differences between starting ethers and their cycloisomerized bicyclic counterparts.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Veronique Michelet
Summary: The field of gold catalysis has been expanding continuously over the past 20 years, with the discovery of several new rearrangements. Key contributions in this area include the pi-activation of unsaturated substrates and the application of aryl, alkyne, alkene, or keto derivatives.
Article
Chemistry, Organic
Vincenzo Marsicano, Antonio Arcadi, Veronique Michelet
Summary: In this study, alkyl- and aryl-substituted N-propargyl phthalimides were used as starting materials to selectively synthesize α-fluoro, β-phthalimido ketones, α,alpha-difluoro, β-phthalimido ketones, or β-phthalimido α-diketones through gold-catalyzed oxyfluorination/oxydifluorination or dioxygenation reactions. Key factors controlling product selectivity were identified, and the simultaneous assembly of the quinoxaline nucleus and removal of the phthalimido-protecting group were tested. Hypothetical reaction mechanisms for different reaction pathways were proposed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Elodie Louisy, Sandra Olivero, Veronique Michelet, Alice Mija
Summary: This study explores the potential of (R)-(+)-limonene, a major byproduct of the citrus industry, as a biobased thermoset precursor. The findings show that cis-LDO can be used to create highly promising biobased epoxy monomers for the production of high-performance thermoset materials.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Review
Chemistry, Organic
Aurelien Dupeux, Veronique Michelet
Summary: This article provides an overview of enantioselective strategies for the synthesis of oxazinoindoles and evaluates the bioactive properties of chiral oxazinoindoles.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Multidisciplinary
Elodie Louisy, Veronika Khodyrieva, Sandra Olivero, Veronique Michelet, Alice Mija
Summary: This paper presents a review of the applications of limonene oxide and dioxide as renewable raw materials for the development of biobased polymers. The polymerization techniques for limonene oxide and dioxide monomers are discussed.
Review
Chemistry, Multidisciplinary
Philippe Martinaux, Romain Laher, Christophe Marin, Veronique Michelet
Summary: This article introduces the application of transition metal-catalyzed cyclization reactions in fragrance synthesis, particularly in the synthesis of key skeletons. These reactions can improve atom economy and synthetic efficiency, providing new alternatives for the fragrance industry.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Romain Melot, Veronique Michelet
Summary: Coinage metals have shown great catalytic activity in organic transformation processes, making them the preferred choice for researchers. This review focuses on the recent development of coinage metal-catalyzed domino reactions using ortho-alkynylaryl and heteroaryl aldehydes and ketones, leading to functionalized heterocycles. The use of gold and silver chiral complexes as catalysts, as well as the preparation methods for chromenes and indoles, are discussed. The review also highlights the applications of copper and ruthenium in cyclization and asymmetric hydrogenation processes.
Article
Chemistry, Multidisciplinary
Kristina Plevova, Laura Juliana Prieto Pabon, Marc Gaysinski, Sophie Poulain-Martini, Veronique Michelet
Summary: Chiral Ag-atropisomeric ligand species were examined in solution at varying temperatures using P-31-NMR spectroscopy. The analysis of key parameters in Ag-BINAP complexes was conducted to understand their significance in an enantioselective transformation. An efficient silver-catalyzed intramolecular [4+2] cycloaddition of amide-1,6-enyne furnished an enantiomerically enriched tricyclic compound under mild reaction conditions using simple reagents.
Article
Chemistry, Applied
Romain Melot, Sandra Olivero, Veronique Michelet
Summary: A synthetic route for alkynylated saturated N-heterocycles was developed via a sequential combination of Shono oxidation and gold(I)-catalyzed alkynylation reaction. The electrochemical Shono oxidation enabled efficient access to various N,O-acetals through direct C-H bond functionalization of cyclic amines. The gold-catalyzed process allowed the introduction of aryl acetylene partners with different electron properties. Promising initial results on asymmetric version were obtained.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Alexis Truchon, Aurelien Dupeux, Sandra Olivero, Veronique Michelet
Summary: A gold-catalyzed orthogonal tandem reaction using HFIP as a Lewis acid has been developed to access carbocyclic ketone on naphthalene substrates. The yield of cyclic ketones ranged from 15% to 91% using a variety of acenaphthylene carbaldehydes. The mechanism involved a cyclization process followed by an [Au]-HFIP interaction for the final rearrangement. The gram-scale transformation and post-functionalization bromination were successfully carried out.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Alice Mija, Elodie Louisy, Sara Lachegur, Veronika Khodyrieva, Philippe Martinaux, Sandra Olivero, Veronique Michelet
Summary: This study valorizes the benign epoxidation of (R)-(+)-limonene to generate novel bio-resourced limonene dioxide monomers. The racemic limonene dioxide was cured with glutaric and dimethylglutaric anhydrides leading to thermosets with a high T-g and good mechanical properties.
Article
Chemistry, Organic
Maxime De Abreu, Yue Tang, Etienne Brachet, Mohamed Selkti, Veronique Michelet, Philippe Belmont
Summary: An efficient silver-catalyzed tandem reaction has been developed for the formation of 1,2-dihydroisoquinoline derivatives, providing a straightforward method to access highly functionalized multiheterocyclic scaffolds. This methodology offers a promising route for the synthesis and development of biologically relevant new heterocyclic pharmacophores, and allows for modifications at various sites of this pharmacophore.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
