Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Daisuke Yokose, Yuki Nagashima, Suzuka Kinoshita, Juntaro Nogami, Ken Tanaka
Summary: Axially chiral styrene-carboxylic esters and stilbenedicarboxylic esters were synthesized with high yields and excellent enantioselectivity using chelation-controlled cycloaddition reactions. The five-membered chelate coordinating to rhodium showed higher reactivity in the reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ryota Shimotsukue, Kohei Fujii, Yu Sato, Yuki Nagashima, Ken Tanaka
Summary: We have developed a rhodium-catalyzed intermolecular [2+2+2] cycloaddition reaction with excellent selectivity, producing chiral cyclohexadienylamines. The reaction involves the reaction of two arylacetylenes with a cis-enamide or a silylacetylene to yield the desired products with complete regio- and diastereoselectivity and high yields and enantioselectivity. Mechanistic studies suggest the formation of a rhodacyclopentadiene intermediate from the terminal alkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
John M. Halford-McGuff, Alexandra M. Z. Slawin, Allan J. B. Watson
Summary: This article presents a predictive model for the reactivity and turnover of the Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and alkynes. Contrary to the proposed electronic model, this model suggests that the reaction is predominantly driven by steric effects, and turnover is proportional to alkyne steric parameters. The model allows for the prediction of catalyst loading, turnover, and reaction yield based on the assessment of the alkyne's steric parameter.
Article
Chemistry, Physical
Takeshi Yasui, Rine Tatsumi, Yoshihiko Yamamoto
Summary: In this study, a dual cobalt and photoredox catalysis was utilized for the [2+2+2] cycloaddition of enediynes to produce tricyclic cyclohexadienes with a quaternary bridgehead carbon. The use of a chiral ligand, (S)-Segphos, enabled highly enantioselective reactions, leading to highly enantio-enriched cyclohexadienes.
Article
Chemistry, Applied
Takeshi Yasui, Yuya Nakazato, Koutarou Kurisaki, Yoshihiko Yamamoto
Summary: In this study, a Rh-catalyzed asymmetric [2+2+2] cycloaddition reaction was reported, resulting in the synthesis of enantio-enriched tricyclic cyclohexadienes with a quaternary bridgehead carbon. It was found that the Rh-Phanephos complex was the most suitable catalyst, while Rh-biaryl bisphosphine catalysts were not applicable.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Biki Ghosh, Mahesh Singh Harariya, Santanu Mukherjee
Summary: The desymmetrization approach enables the construction of centrally chiral unfunctionalized arenes from unsymmetrically substituted arene rings. This approach is based on a [4+2]-cycloaddition reaction and greatly simplifies the synthesis of chiral arenes with outstanding enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ming Zhang, Xiao-Chen Wang
Summary: This method presents a mild and efficient approach for synthesizing enantioenriched tetrahydroquinoline-fused cyclobutenes through a cascade reaction, catalyzed by chiral spiro-bicyclic bisboranes. The bisboranes function by catalyzing hydride transfer and activating the alkynone substrate for an enantioselective cycloaddition reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kai Wang, Xiangfeng Lin, Yan Liu, Can Li
Summary: This study presents a novel catalytic asymmetric [4+2] cycloaddition reaction, achieved through direct allylic C-H functionalization with high diastereoselectivities and enantioselectivities to synthesize hydroquinolines.
Article
Chemistry, Multidisciplinary
Guanghao Huang, Regis Guillot, Cyrille Kouklovsky, Boris Maryasin, Aurelien de la Torre
Summary: A broadly applicable diastereo- and enantioselective inverse-electron-demand Diels-Alder reaction of 2-pyrones and acyclic enol ethers is reported, leading to the synthesis of bridged bicyclic lactones with high yields and enantioselectivities using a copper(II)-BOX catalytic system. Mechanistic studies suggest a stepwise mechanism, and the synthetic potential of the bridged bicyclic lactones is demonstrated through the enantioselective synthesis of polyfunctional cyclohexenes and cyclohexadienes, as well as a carbasugar unit.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Sundaravel Vivek Kumar, Patrick J. Guiry
Summary: We have developed a facile synthetic route for a novel series of imidazolinyl-[2.2]paracyclophanol (UCD-Imphanol) ligands with central and planar chirality. These ligands showed excellent activities and selectivities in asymmetric reactions, leading to enantioenriched pyrrolidines with high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Yoshimi Kato, Luqing Lin, Masahiro Kojima, Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: By introducing pseudo-C2 symmetric tunable chiral carboxylic acids, the study achieved enantioselective C(sp(3))-H amidation reactions of substrates such as 2-alkylpyridines, improving the chiral selectivity towards the substrates.
Article
Chemistry, Physical
Hui Yang, Ru Zhang, Su-Zhen Zhang, Qing Gu, Shu-Li You
Summary: Researchers have developed a series of chiral spiro ligands (BCSCp) from commercially available and cheap Bisphenol C, and prepared their corresponding rhodium complexes. These complexes have been successfully applied in enantioselective aryl C-H addition to nitroalkenes, producing C-H adducts with yields up to 88% and ee up to 98%.
Article
Chemistry, Multidisciplinary
Hui Yang, Zi-Qi Yang, Su-Zhen Zhang, Wen-Wen Zhang, Qing Gu, Shu-Li You
Summary: Chiral dihydrobenzofuran is a valuable synthetic fragment in both medicinal and organic chemistry. Efficient rhodium(III)-catalyzed chemoselective and enantioselective C-H functionalization/[3+2] annulation of N-phenoxyacetamides with 1,3-dienes is reported. In the presence of 5 mol% CpRh complex, various chiral dihydrobenzofurans were synthesized in up to 79% yield and 98% ee. This reaction proceeds under mild conditions with excellent functional group compatibility.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Physical
Anna, Zhaohang Chen, Hongwei Qiao, Juanhong Gao, Mengyao Zhu, Chao Li
Summary: A series of xanthone derivatives were synthesized by rhodium-catalyzed cycloaddition and sequential oxidation, demonstrating wide applicability. The derivatives showed excellent yields and different substituent electron effects, highlighting the potential of the proposed approach. The successful one-pot synthesis from 1ethynyl-2-phenoxybenzene further emphasized the attractiveness of the current method for xanthone synthesis.
CATALYSIS COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Chandrasekar Praveen, Aurelien Dupeux, Veronique Michelet
Summary: The review discusses the catalytic activity of gold in functionalizing various C-H bonds with high selectivity, highlighting factors such as steric/electronic properties of C-H bonds, oxidation state of gold, and stereoelectronic capacity of coordinated ligands. It also reveals the potential applications of Au(I) and Au(III) species in regio- and site-selective activation of challenging C-H bonds, as well as the selective C-H bond activation with different heterocycles described in recent literature.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
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, 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)