Article
Chemistry, Organic
Zhi-Bang Huang, Ming-Hao Zhao, Xu Liu, Lijia Wang
Summary: An indium catalyzed Prins/Friedel-Crafts tandem cyclization reaction has been developed, providing an efficient and practical method for the construction of various polycyclic indole frameworks with high diastereoselectivity and good functional group tolerance (30 examples, up to 98% yield with >95 : 5 dr). The resulting products are easily accessible for further chemical transformations.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Dwaipayan Das, Agniva Das, Saiful Islam, Asish R. R. Das, Adrita Banerjee, Romit Majumder, Debasish Bandyopadhyay
Summary: An efficient and intriguing method using Rh(II) catalysis has been developed for the preparation of fused furan moieties. The technique involves a one-pot C-H activation/concomitant tandem annulation process using an enolic compound and a beta-keto sulfoxonium ylide as reactants. The synthesis only requires Rh-2(TFA)(4) as the catalyst, removing the need for additional metallic or nonmetallic additives. This transformation of naphthoquinone fused furan into highly decorated naphthoquinone fused indolizines shows great promise in synthetic applications.
Article
Chemistry, Organic
Takanori Shibata, Mio Sasaki, Masafumi Kojima, Mamoru Ito
Summary: The chiral Ir(I)-catalyzed intermolecular reaction of N-carbamoylpyrrole and indole derivatives with alpha,beta-unsaturated carbonyl compounds proceeded with high enantioselectivity, yielding chirally functionalized pyrroles and indoles as formal C-H conjugate adducts. The reaction mechanism was further investigated through deuterium labeling experiments.
Article
Chemistry, Organic
Takanori Shibata, Natsumi Shiozawa, Shun Nishibe, Hideaki Takano, Satoshi Maeda
Summary: A chiral Pt(ii) complex was synthesized and used as an efficient catalyst for an intramolecular [4 + 2] cycloaddition reaction of biphenylenes, resulting in high yields and enantioselectivity at ambient temperature. DFT calculations revealed a Pt(ii)/(iv) cycle involving oxidative addition of biphenylene and C-C bond cleavage.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Haeun Park, Sunwoo Lee
Summary: The Friedel-Crafts acylation reaction was conducted between activated amides and arenes using [Pd(cinnamyl)Cl](2) and Cu(OTf)(2) as catalysts. A variety of N-phenyl-N-tosylbenzamides with substituted phenyl rings underwent reactions with different arenes, including mesitylene, toluene, anisole, 4-tert-butylbenzene, o-xylene, m-xylene, and p-xylene, resulting in the corresponding diaryl ketones with yields ranging from 49% to 89%.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Huimiao Zhang, Patrick H. Toy
Summary: A halogen bond donor based on a 2,2'-bipyridine framework has been synthesized and used to catalyze Friedel-Crafts reactions of furans, yielding good reaction yields with moderate catalyst loading at low temperatures. The catalyst design allows for the potential development of an enantioselective version for stereo-selective catalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Kaikai Wang, Rong Zeng
Summary: This study presents a photoinduced iron catalysis that efficiently cleaves C-C bonds and brominates or iodinates unstrained tertiary cycloalkanols using NBS/NIS. The reaction demonstrates good functional group tolerance and high yields under mild conditions, providing a powerful tool for the synthesis of remote halogenated alkyl ketones. The resulting products can be further converted to valuable molecules through nucleophilic substitution or cross-coupling reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Satheesh Borra, Hun Young Kim, Kyungsoo Oh
Summary: A one-pot tandem approach to [1,2,3]triazolo[1,5-a]quinolines was developed from (E)-s-chlorovinyl ketones and 2-azidoaryl carbonyls using a sequence of alpha-vinyl aldol and azide- alkyne cycloaddition reactions. The intramolecular azide-alkyne cycloaddition of allenol intermediates was promoted by NEt3 and nickel catalysts. The [1,2,3]triazolo[1,5-a]quinolines are important precursors to alpha-diazoimines and can provide valuable heterocyclic compounds through denitrogenative transformations.
Article
Chemistry, Organic
Xi Xiao, Xiaobiao Lu, Ming Zhang, Haoqing Hou, Changfeng Wan, Jinbiao Liu
Summary: A novel synthetic method was successfully developed for the preparation of multisubstituted dihydrochromeno[2,3-b]indole derivatives in moderate to high yields using a catalytic environmentally benign iron salt.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Juan J. Rojas, Elena Torrisi, Maryne A. J. Dubois, Riashat Hossain, Andrew J. P. White, Giovanni Zappia, James J. Mousseau, Chulho Choi, James A. Bull
Summary: This paper reports a method for synthesizing 1,4-dioxanes and explores the catalytic mechanism of the reaction. The reaction exhibits high regio- and diastereoselectivity, and the resulting products serve as interesting motifs for drug discovery.
Article
Chemistry, Multidisciplinary
Felipe Verdugo, Ricardo Rodino, Martin Calvelo, Jose Luis Mascarenas, Fernando Lopez
Summary: The reactivity of carbonyl-tethered alkylidenecyclopropanes (ACPs) can be directed towards tandem cycloisomerization/cross-coupling processes by using Pd-0 catalysts with phosphorus-based monodentate ligands. This allows for the synthesis of a wide variety of highly functionalized cyclic alcohols and amines through the formation of key pi-allyl oxapalladacyclic intermediates which are trapped with external nucleophilic partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yunlong Zhao, Rou Xiao, Weibin Fang, Junling Zhao
Summary: This study presents a protocol for the highly selective addition reaction of isatin-derived beta,gamma-unsaturated alpha-ketoesters with 4-aminoindoles at the C7 position. The reaction, catalyzed by a SPINOL-derived chiral phosphoric acid, yields bisindole derivatives with up to 97% enantiomeric excess. Further biological testing revealed that the products have high cytotoxicity against various cancer cell lines.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Tsukasa Inishi, Goki Hirata, Takashi Nishikata
Summary: Indoles are found to undergo Michael additions efficiently under the catalysis of a cationic iron salt, allowing smooth reactions with beta-mono- and disubstituted enones. The highly active cationic iron catalyst achieves a maximum TON of 425, and enables chemoselective Michael additions of substrates containing both enone and alpha,beta-unsaturated ester moieties.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Jodie L. Hann, Catherine L. Lyall, Gabriele Kociok-Kohn, Simon E. Lewis
Summary: This study presents a method for the synthesis of N-alkoxycarbonyl pyrroles by the condensation of readily available O-substituted carbamates with 2,5-dimethoxytetrahydrofuran. It is demonstrated that N-alkoxycarbonyl protection can impart distinct reactivity to pyrrole in comparison with N-sulfonyl protection.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Ryoya Tajima, Takaaki Saito, Takayoshi Arai
Summary: The conventional acid-catalyzed aza-Friedel-Crafts reaction of phenols with imines typically shows ortho-selectivity. However, a chiral bis(imidazolidine) pyridine (PyBidine)-Ni(OAc)(2) catalyst can switch the regioselectivity to para-selectivity. This switch is facilitated by the bulky PyBidine-Ni(OAc)(2) catalyst with a Ph2CHCH2 substituent, resulting in highly para-selective aza-Friedel-Crafts reactions (up to 99:1 para/ortho selectivity).
Article
Chemistry, Multidisciplinary
Sascha Jahnigen, Katia Le Barbu-Debus, Regis Guillot, Rodolphe Vuilleumier, Anne Zehnacker
Summary: In this study, the effect of a twofold screw axis on the solid-state VCD spectrum was investigated using both experimental and theoretical analysis. It was found that the VCD spectrum can reflect the supramolecular chirality of the crystal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chanjuan Zhang, Philipp Gotico, Regis Guillot, Diana Dragoe, Winfried Leibl, Zakaria Halime, Ally Aukauloo
Summary: At the core of carbon monoxide dehydrogenase (CODH) active site, two metal ions and hydrogen bonding from amino acids facilitate the interconversion between CO2 and CO. A designed molecular catalyst with a bimetallic iron complex and hydrogen bonding interactions showed improved selectivity and stability in heterogeneous CO2 reduction to CO. X-ray structures revealed the compromise between rigidity and flexibility of the catalyst in accommodating CO2 capture, activation, and reduction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Juba Ghouilem, Sokna Bazzi, Nicolas Grimblat, Pascal Retailleau, Vincent Gandon, Samir Messaoudi
Summary: This study presents a novel method for the Pd(ii)-catalyzed arylation of 3-aminosugars using a transient directing group (TDG) approach combined with an external 2-pyridone ligand. The released free amine is transformed into an azide function, which is further utilized in a CuAAC reaction to generate complex substituted C3-triazolo C-glycosides with high yields.
CHEMICAL COMMUNICATIONS
(2023)
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, Multidisciplinary
Audrey Mauger, Maxime Jarret, Aurelien Tap, Remi Perrin, Regis Guillot, Cyrille Kouklovsky, Vincent Gandon, Guillaume Vincent
Summary: We synthesized highly strained pentacyclic caged framework of mavacuran alkaloids and successfully achieved the concise total synthesis of C-fluorocurine, C-profluorocurine, C-mavacurine, normavacurine, 16-epi-pleiocarpamine and taberdivarine H. A strategy involving late-stage Michael addition and intermolecular 1,4-addition reactions was designed. The first total syntheses of C-profluorocurine and C-fluorocurine were achieved through dihydroxylation of C-mavacurine and a pinacol rearrangement, respectively.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Vivek W. Bhoyare, E. Daiann Sosa Carrizo, Chetan C. Chintawar, Vincent Gandon, Nitin T. Patil
Summary: In this study, we present a ligand-enabled gold (Au) catalyzed Heck reaction using Au(I)/Au(III) redox catalysis. For the first time in gold chemistry, essential organometallic steps such as migratory insertion and s-hydride elimination have been achieved in a catalytic manner. This methodology not only overcomes the limitations of previous transition metal-catalyzed Heck reactions, such as the need for specialized substrates and the formation of a mixture of regioisomeric products due to undesirable chain-walking, but also provides complementary regioselectivity compared to other transition metal catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Stephanie Solier, Sebastian Mueller, Tatiana Caneque, Antoine Versini, Arnaud Mansart, Fabien Sindikubwabo, Leeroy Baron, Laila Emam, Pierre Gestraud, G. Dan Pantos, Vincent Gandon, Christine Gaillet, Ting-Di Wu, Florent Dingli, Damarys Loew, Sylvain Baulande, Sylvere Durand, Valentin Sencio, Cyril Robil, Francois Trottein, David Pericat, Emmanuelle Naeser, Celine Cougoule, Etienne Meunier, Anne-Laure Begue, Helene Salmon, Nicolas Manel, Alain Puisieux, Sarah Watson, Mark A. Dawson, Nicolas Servant, Guido Kroemer, Djillali Annane, Raphael Rodriguez
Summary: Inflammation is a complex physiological process that involves immune cells clearing sources of injury. Excessive inflammation is associated with infection and several diseases. The cell surface glycoprotein CD44 mediates the uptake of metals, including copper, and affects the metabolic and epigenetic states involved in inflammation.
Article
Chemistry, Organic
Dayi Liu, Zeynab Imani, Catherine Gourson, Regis Guillot, Sylvie Robin, David J. J. Aitken
Summary: Post-synthetic modification is a powerful technique for accessing noncanonical peptide derivatives selectively, but it has not been used for installing multiple arrays of modified side chains. In this study, we applied this approach in solution phase to prepare short N- and C-capped homooligomers of 3-amino-1-methylazetidine-3-carboxylic acid with all azetidine side chain functions in the free amine form. The key step involved multiple reductive amination reactions of the corresponding post-synthetically deprotected secondary amines.
Article
Chemistry, Physical
Arghadip Ghosh, Nicolas Grimblat, Somratan Sau, Arijit Saha, Vincent Gandon, Akhila K. Sahoo
Summary: This article presents a Pd-(II)-catalyzed direct difunctionalization of two C-(sp(3))-H bonds of aliphatic carboxylic acid derivatives using bifunctional reagents (BFRs) of the 2-iodobenzoic acid series. Various directing groups, ligands, bases, and co-oxidants are employed to facilitate the reaction, leading to the formation of benzo-fused peripheral-substituted caprolactones. Mechanistic studies provide insights into the crucial steps involved in the transformation. The versatility of the complex molecular entities is also showcased.
Article
Chemistry, Multidisciplinary
Arghadip Ghosh, Koneti Kondalarao, Arijit Saha, Vincent Gandon, Akhila K. Sahoo
Summary: A tandem three-component C-H bond addition involving the activation of an inert C(sp(3))-H bond is reported. The reaction enables the direct regioselective synthesis of 1,2-difunctionalized arenes. Mechanistic studies reveal the reaction pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Somratan Sau, Kallol Mukherjee, Koneti Kondalarao, Vincent Gandon, Akhila K. Sahoo
Summary: A chiral sulfoximine-enabled Ru-(II)-catalyzed asymmetric C-H activation/functionalization process has been developed for the synthesis of dihydrobenzofuran- or indoline-fused isoquinolinones with a tertiary or quaternary stereocenter. The method achieves high yields and enantioselectivities (up to 97:3 enantiomeric ratio) and allows for the recovery and reuse of the chiral sulfoxide precursor.
Article
Chemistry, Organic
Dayi Liu, Regis Guillot, Sylvie Robin, David J. Aitken
Summary: In this study, trans-3-benzyloxycarbonylamino-1-methyl-3-(methylcarbamoyl)azetidine-1-oxide was successfully synthesized by stereoselective oxidation. The stable molecule was characterized in solution and solid state, revealing different intramolecular and intermolecular hydrogen bonding patterns.
Article
Chemistry, Inorganic & Nuclear
Diana Cebotari, Sergiu Calancea, Jerome Marrot, Regis Guillot, Clement Falaise, Vincent Guerineau, David Touboul, Mohamed Haouas, Aurelian Gulea, Sebastien Floquet
Summary: This paper reports the synthesis and characterization of six coordination complexes obtained by reacting [MoV2 O2S(2)](2+) clusters with bisthiosemicarbazone ligands containing flexible or rigid spacers. The nuclearity of the complexes was found to be controlled by the nature of the spacer between the thiosemicarbazone units, as revealed by structural characterization techniques. Flexible spacers resulted in binuclear complexes [MoV2 O2S2(L1-3)], while rigid spacers led to tetranuclear complexes [(MoV2 O2S2)(2)(L4-6)(2)].
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jean-Noel Rebilly, Christian Herrero, Katell Senechal-David, Regis Guillot, Frederic Banse
Summary: The catalytic properties of an iron complex with a pentadentate cross-bridged ligand backbone were investigated. It exhibited moderate conversions in epoxidation and alkane hydroxylation with H2O2 as the oxidant, and satisfactory conversions in aromatic hydroxylation. However, the addition of acid to the reaction medium significantly enhanced the oxidation of aromatics and alkenes. Spectroscopic analysis revealed that the accumulation of the expected Fe-III(OOH) intermediate was limited under these conditions, unless an acid was present, which was attributed to the inertness induced by the cross-bridged ligand backbone that was partly reduced under acidic conditions.
DALTON TRANSACTIONS
(2023)
