Article
Chemistry, Multidisciplinary
Casper L. Barlose, Niklas L. ostergaard, Rene S. Bitsch, Marc V. Iversen, Karl Anker Jorgensen
Summary: An enantioselective methodology for constructing trans-Diels-Alder scaffolds with up to five contiguous stereocenters is presented, utilizing a halogen effect and a novel discovered pseudo-halogen effect. The reaction involves an endo-selective, secondary-amine catalyzed Diels-Alder reaction followed by a subsequent S(N)2-like reaction at a tertiary center to obtain the trans-Diels-Alder scaffold. The mechanism was supported by experimental results and computational studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Flemming Heinen, Dominik L. Reinhard, Elric Engelage, Stefan M. Huber
Summary: This study presents the first application of a bidentate bis(iodolium) salt as an organocatalyst in various reactions, surpassing the performance of iodine(I)-based organocatalysts and approaching that of strong Lewis acids like BF3. Coordination of the bidentate XB donor to the substrate was confirmed through structural analysis and DFT calculations of the transition states.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Ruyu Xie, Zhiqiang Zhao, Yongxing Zhao, Rui Li, Jinzhong Yao, Maozhong Miao
Summary: Via Cu(I)-catalyzed cycloisomerization, readily available allenyl ketones bearing a cyclopropyl moiety can form in situ furan-fused cyclobutenes, which are highly reactive and powerful species that can undergo annulative fragmentation with terminal ynones to produce a wide variety of functional furans in moderate to high yields. This ring-distortion protocol features an unprecedented strain-controlled cycloisomerization/Diels-Alder/retro-Diels-Alder (CDRD) sequence under mild conditions.
Article
Chemistry, Organic
Jian-Xiang Zhu, Fu Pi, Teng Sun, Wen-Yu Huang, Lu Gao, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: This article introduces a palladium-catalyzed tandem reaction that proceeds through sequential 2,4-dienylation/Michael addition/pi-sigma-pi isomerization/allylic alkylation. Using ortho-functionalized aryl enones and 2,4-dienyl carbonates as substrates, enantioenriched architectures with fused and spirocyclic frameworks are constructed in moderate to excellent yields and stereoselectivity. Importantly, the intrinsic intramolecular Diels-Alder reaction pattern of the dienylated intermediates is effectively reversed via Pd(0)-pi-Lewis base catalysis.
Article
Chemistry, Multidisciplinary
Tibor Penaska, Viktoria Modrocka, Klara Stankovianska, Maria Meciarova, Erik Rakovsky, Radovan Sebesta
Summary: This study achieves enantioselective and diastereoselective synthesis of densely substituted chiral pyran derivatives by using amino-thiourea or quinine organocatalyst under ball-milling conditions. Liquid-assisted grinding proves to be a highly efficient means of obtaining pyrans in high yield, with high enantiomeric purities and short reaction times.
Article
Chemistry, Multidisciplinary
Zhimei Mao, Aimin Huang, Lin Ma, Min Zhang
Summary: A facile visible light-promoted approach has been developed for the synthesis of anthracenone-furans from readily available 2,3-dibromonaphthoquinones and phenylbenzofurans via a formal Diels Alder reaction. This reaction involves wavelength-selective agitation of 4CzIPN, energy transfer to quinones, recombination of 1,6-biradicals, and elimination to give anthracenone-furans in good to excellent yields in one pot.
Article
Chemistry, Multidisciplinary
Xin-Qi Zhu, Qian Wang, Jieping Zhu
Summary: This study reports chiral phosphoric acid-catalyzed enantioselective Diels-Alder reactions and three-component reactions, which can efficiently synthesize compounds with multiple functional groups in high yields and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Daniel P. Schwinger, Thomas Pickl, Thorsten Bach
Summary: Cyclohept-1-ene-1-carbaldehyde undergoes photoinduced E & RARR; Z isomerization at & lambda; =350 nm. The ring strain facilitates various reactions, including Diels-Alder cycloadditions, [3 + 2] cycloadditions, and enereactions. The products obtained are trans-fusedat the cycloheptane core and yield up to 82%. Single crystal X-ray analyses confirm the structure and relative configuration. In the presence of BF3 and 2,3-dimethylbuta-1,3-diene, cyclohept-1-ene-1-carbaldehyde undergoes a stereoselective rearrangement to form a tricyclic ketone (87%).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
David M. Malouf, Abigail D. Richardson, Scott J. L'Heureux, Elizabeth A. McDonough, Ava M. Henry, Jerry Y. Sheng, Erica A. Medhurst, Angel E. Canales, Cameron J. Fleischer, Ty B. Cecil, Spencer E. Thurman, Cameron C. McMullen, Philip J. Costanzo, Daniel A. Bercovici
Summary: In this study, Ylidenenorbornadienes (YNDs) were prepared by [4 + 2] cyclo-additions and were found to react with beta-mercaptoethanol to yield a mixture of four diastereomers. These diastereomers exhibited retro-[4 + 2] cycloaddition at different rates. The rate constants of the diastereomers were extrapolated using a simulated kinetics approach. The fragmentation of YNDs showed a wide variability in rate, depending on the stereoelectronics of the ylidene substituents. Notably, a substrate containing one carboxylic ester exhibited exceptional stability to fragmentation.
Article
Chemistry, Organic
Yuan-Yuan Xu, Lei Dai, Zhong-Hua Gao, Song Ye
Summary: The e-benzylation of gamma-alkenyl-gamma-oxidized enals via dual photoredox and N-heterocyclic carbene catalysis has been developed, providing moderate to good yields of e-benzyl-alpha,fi-gamma,(5-bisunsa-turated esters with exclusive regioselectivities. The reaction is proposed to proceed through the generation of a benzyl radical under photocatalysis, followed by its addition to an NHC-bound trienolate intermediate.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Miglena K. Georgieva, A. Gil Santos
Summary: The Diels-Alder reaction is a fascinating chemical process that has been extensively studied, both in its achiral and chiral versions. In this study, the authors investigate the Diels-Alder reaction of 2'-hydroxychalcones with two dienes, catalyzed by chiral organo-boron Lewis acid complexes. The authors use theoretical methods to evaluate the proposed reaction mechanism and provide insights into the enantioselectivity and endo/exo selectivity of the reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Gangming Xu, Suiqun Yang
Summary: Natural [4 + 2]-cyclases play a crucial role in the biosynthesis of natural products, with microbial [4 + 2]-cyclases exhibiting structural diversity and a broad substrate range. The evolutionary history and catalytic mechanisms of these cyclases, with 52 characterized so far, remain unclear.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2021)
Article
Chemistry, Multidisciplinary
Masao Ohashi, Dan Tan, Jiayan Lu, Cooper S. Jamieson, Daiki Kanayama, Jiahai Zhou, K. N. Houk, Yi Tang
Summary: The synthesis of cis-decalin structures using [4 + 2] cycloaddition with high stereoselectivity is challenging. In this study, we investigated the biosynthetic pathway of the fungal natural product fischerin (1) and identified a novel pericyclase, FinI, which catalyzes this reaction. The cocrystal structure of FinI, a predicted O-methyltransferase, with the product and SAM provides valuable insights into the natural formation of cis-decalin.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Guang-Chao Feng, Jun-Chi Li, Xiang Huang, Ji-Kai Liu, Bin Wu, Jin-Ming Yang
Summary: A novel cascade gold(I)-catalyzed hydroarylation of alkynylindoles and subsequent Diels-Alder cycloaddition with electron-deficient alkynes and alkenes is reported herein. The method features low catalyst loadings, high regioselectivity, broad functional group tolerances, access to important heterocycles, and 100% atom economy.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Julia O. Strelnikova, Alexander N. Koronatov, Nikolai Rostovskii, Alexander F. Khlebnikov, Olesya Khoroshilova, Mariya A. Kryukova, Mikhail S. Novikov
Summary: The domino reaction catalyzed by Rh-2(Piv)(4) leads to the formation of N-sulfonylated (Z)-2-(2-aminovinyl)imidazoles, providing a direct and flexible access to the desired compounds.
Article
Chemistry, Multidisciplinary
Benoit Bertrand, Candice Botuha, Jeremy Forte, Heloise Dossmann, Michele Salmain
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Organic
Anissa Beghennou, Kevin Passador, Anthony Passador, Vincent Corce, Serge Thorimbert, Candice Botuha
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Inorganic & Nuclear
Benoit Bertrand, Geoffrey Gontard, Candice Botuha, Michele Salmain
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Liang Chang, Nathalie Fischer-Durand, Geoffrey Gontard, Benoit Bertrand, Serge Thorimbert, Luc Dechoux
Summary: A novel dearomatization reaction for nitrogen-containing heterocycles was developed, utilizing biorenewable methyl coumalate as an efficient partner under solvent-free conditions. This reaction successfully converted nine types of basic aromatic rings into their pyrido[1,2-a] fused derivatives, with good to excellent yields. The fluorescence properties of the products were harnessed for conjugating fluorescent tags to bovine serum albumin (BSA) and immunoglobulin G.
Article
Chemistry, Medicinal
Robin Ramos, Jean-Francois Gilles, Romain Morichon, Cedric Przybylski, Benoit Caron, Candice Botuha, Anthi Karaiskou, Michele Salmain, Joelle Sobczak-Thepot
Summary: IrBDP, a half-sandwich complex of iridium(III), containing a fluorescent and lipophilic BODIPY reporter group, is being developed as a potential anticancer drug candidate. Studies show that IrBDP quickly permeates the plasma membrane and accumulates in the mitochondria and endoplasmic reticulum, leading to cellular response and potential cytotoxicity.
JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Organic
Sawsen Cherraben, Jeremy Scelle, Bernold Hasenknopf, Guillaume Vives, Matthieu Sollogoub
Summary: A family of cyclodextrins functionalized with different numbers of amines can control the rate of their threading and dethreading on a molecular axle based on pH and substitution pattern. The uniqueness of this system lies in the ability to directly control the switch rate by operating the stimulus on the macrocycle.
Article
Chemistry, Multidisciplinary
Jeremy Scelle, Hugo Vervoitte, Laurent Bouteiller, Lise-Marie Chamoreau, Matthieu Sollogoub, Guillaume Vives, Bernold Hasenknopf
Summary: The encapsulation of guests in a confined space can lead to unusual conformations and reactivities. This study focuses on the effect of a cyclodextrin (CD) dimer cavity on the conformation of alpha,omega-alkyl-diphosphate axles in pseudorotaxane architectures. Results show that in both solid and solution states, the CD can compress the alkyl chain, resulting in conformational changes.
Article
Chemistry, Organic
Alexander Mamontov, Liang Chang, Heloise Dossmann, Benoit Bertrand, Luc Dechoux, Serge Thorimbert
Summary: In this study, commercially available Fe(TTP)Cl catalyst was used to catalyze the three-component dearomative formal cycloaddition reactions between pyridines, diazo compounds, and coumalates at room temperature. Diversely substituted annelated seven-membered N-heterocycles could be synthesized in less than 10 minutes with high efficiency. The study also demonstrated the successful substitution of benzimidazoles for pyridines in this reaction.
Article
Materials Science, Multidisciplinary
Anthony Nina-Diogo, Benoit Bertrand, Serge Thorimbert, Geoffrey Gontard, Sehr Nassem-Kahn, Andrea Echeverri, Julia Contreras-Garcia, Clemence Allain, Gilles Lemercier, Eleonora Luppi, Candice Botuha
Summary: This report presents the design, synthesis, and photophysical study of two new series of promising fluorescent trisubstituted triazoles, PyOHTr and PyCOTr. The PyOHTr molecules were found to exhibit an excited state intramolecular proton transfer (ESIPT) fluorescence mechanism through ab initio theoretical calculations. These fluorescent dyes possess unique optical properties with potential applications in medicinal chemistry and materials science.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Organic
Anissa Beghennou, Geoffrey Gontard, Heloise Dossmann, Kevin Passador, Serge Thorimbert, Vincent Corce, Candice Botuha
Summary: Efficient synthesis of original 1,6-naphthyridin-7(6H)-ones and their optical properties, including dual fluorescence, solvatochromism, acidochromism, large Stokes shifts, and high quantum yields, are described in this study. These properties make them suitable for biological applications or as luminescent devices in materials science.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Andrea Echeverri, Candice Botuha, Tatiana Gomez, Eleonora Luppi, Julia Contreras-Garcia, Carlos Cardenas
Summary: Fluorescent probes that can sense the biological medium are extremely important in medical diagnostics. This paper showcases the in-silico design of potential fluorescent biomarkers that fulfill two important conditions - emission wavelength within the optical window of 650 to 950 nm and a large Stokes shift, greater than 150 nm.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Robin Ramos, Jeremy M. Zimbron, Serge Thorimbert, Lise-Marie Chamoreau, Annie Munier, Candice Botuha, Anthi Karaiskou, Michele Salmain, Joelle Sobczak-Thepot
DALTON TRANSACTIONS
(2020)
Article
Chemistry, Inorganic & Nuclear
Benjamin Doistau, Lorien Benda, Jean-Louis Cantin, Olivier Cador, Fabrice Pointillart, Wolfgang Wernsdorfer, Lise-Marie Chamoreau, Valerie Marvaud, Bernold Hasenknopf, Guillaume Vives
DALTON TRANSACTIONS
(2020)
