Article
Chemistry, Multidisciplinary
Pengwei Ji, Xiaopei Liu, Jiwei Xu, Xu Zhang, Jianhua Guo, Wen-Wen Chen, Baoguo Zhao
Summary: This study successfully achieved the direct asymmetric functionalization of the inert alpha C-H bonds of N-unprotected propargylic amines using a chiral pyridoxal as a carbonyl catalyst. The method showed high yields and excellent stereoselectivities, providing a solution to a major challenge in organic chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Pengwei Ji, Jianyu Li, Yuhang Tao, Mingzhe Li, Weibo Ling, Jianfeng Chen, Baoguo Zhao
Summary: By using a biomimetic organocatalyst, a direct asymmetric α-alkylation of NH2-unprotected amino acid esters with alkyl halides was achieved, leading to the formation of chiral quaternary α-amino acid esters in high yields (up to 99%) and high enantioselectivities (99% ee) without the need for protecting groups.
Article
Chemistry, Multidisciplinary
Andreas C. Hans, Patrick M. Becker, Johanna Haussmann, Simon Suhr, Daniel M. Wanner, Vera Lederer, Felix Willig, Wolfgang Frey, Biprajit Sarkar, Johannes Kaestner, Rene Peters
Summary: This article discloses a catalyst type that enables highly efficient direct 1,4-additions. The catalyst is a zwitterionic entity, with acetate binding to negatively charged Cu-II and serving as a counterion for benzimidazolium. All three functionalities are involved in the catalytic activation. The productivity of maleimides increased by a factor greater than 300 compared to the literature (TONs up to 6700). High stereoselectivity and productivity were achieved for a wide range of other Michael acceptors as well. The polyfunctional catalyst, accessible in only 4 steps from N-Ph-benzimidazole with an overall yield of 96%, remained robust during catalysis, allowing for multiple reuse with nearly constant efficiency. Mechanistic studies, particularly using DFT, provided a detailed understanding of how the catalyst operates. The benzimidazolium unit stabilizes the coordinated enolate nucleophile and prevents the dissociation of acetate/acetic acid from the catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jing Wang, Wenji Wang, Xiongyu Yang, Jingwen Liu, Haizhou Huang, Mingxin Chang
Summary: In this study, a practical homogeneous direct reductive amination (DRA) procedure using iridium catalysis was reported. The reaction conditions were mild and additive-free, allowing for the formation of structurally and functionally diverse amine products, including drugs and compounds from late-stage manipulation. DFT studies revealed that the reaction proceeds via an outer-sphere H-addition pathway with important roles played by pi-pi interactions and H-bonding.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Julia C. Reisenbauer, Ann-Sophie K. Paschke, Jelena Krizic, Bence B. Botlik, Patrick Finkelstein, Bill Morandi
Summary: Recent advances in single-atom insertion reactions have provided new synthetic approaches for molecular diversification. Directly transforming biologically relevant molecules without prefunctionalization is crucial for expanding the scope and utility of these transformations. This study reports the direct access to quinazolines and pyrimidines from unprotected 1H-indoles and 1H-pyrroles using lithium bis-(trimethylsilyl)-amide (LiHMDS) as a nitrogen source with commercially available hypervalent iodine reagents. The potential of this strategy in lead structure diversification campaigns is demonstrated in late-stage settings.
Review
Chemistry, Multidisciplinary
Daniel J. Scott
Summary: For many years, researchers have been studying the chemistry of white phosphorus in the hopes of finding direct methods for its conversion into useful phosphorus-containing products. Although interesting reactions have been discovered, their practical application has been limited. Recent reports, however, have shown that simple and practical synthetic methods can be used to directly obtain relevant compounds from white phosphorus, marking a significant breakthrough in the field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Shuai Yao, Xiaowei Zhao, Xu Ban, Tianju Shao, Yanli Yin, Weigao Hu, Zhiyong Jiang
Summary: Radical-based functionalization-oriented construction (FoC) is a powerful method for the direct synthesis of imine-containing azaarene derivatives. In this study, a novel FoC method was developed for the direct synthesis of highly functionalized pyrroles. This method involves the reaction of α-amino acids with easily accessible α/β-azaarene-substituted enones under visible light irradiation and with the presence of p-toluenesulfonic acid as an additive.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Dawid Drelinkiewicz, Richard J. Whitby
Summary: A robust and versatile protocol for the synthesis of 1-monosubstituted and 1,4-disubstituted 1H-1,2,3-triazoles was established under continuous flow conditions using copper-on-charcoal as a heterogeneous catalyst. This method allows for the synthesis of a diverse set of substituted 1,2,3-triazoles with good functional group tolerance and high yields, and it has been successfully used to synthesize an antiepileptic agent.
Article
Chemistry, Multidisciplinary
Le'an Hu, Yuan-Zheng Wang, Lei Xu, Qin Yin, Xumu Zhang
Summary: A highly selective catalytic reaction has been developed for the efficient synthesis of chiral unnatural amino acid derivatives. The method features easily accessible substrates, good functional group tolerance, and excellent enantiocontrol, making it applicable for the synthesis of various organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hao-Ran Shen, Chao-Xing Li, Xin Jiang, Yao Lin, Jian-Hua Liu, Fang Zhu, Zhu-Lian Wu, Tian Cai, Wei Wen, Rong-Xing He, Qi-Xiang Guo
Summary: This study reported on a highly efficient aldehyde-catalyzed direct alpha-hydrocarbylation of N-unprotected amino acid esters with aryl-, allyl-, and benzyl halides. By using a chiral BINOL-aldehyde catalyst or a combination of a chiral aldehyde and Lewis acid ZnCl2 as catalysts, the reactions proceeded smoothly, resulting in moderate-to-high yields and good-to-excellent enantioselectivities. The asymmetric alpha-arylation reaction could be used in the formal synthesis of the clinical candidate compound (+)-AG-041R. Based on control experiments, three reaction models were proposed to explain the stereoselective-control outcomes.
Article
Polymer Science
Gokhan Sagdic, Ozgun Daglar, Ufuk Saim Gunay, Emrah Cakmakci, Gurkan Hizal, Umit Tunca, Hakan Durmaz
Summary: Phosphorus-containing polymers are widely used in bio-related applications. This study presents a method to synthesize phosphorylated polymers using a metal-free azide-alkyne cycloaddition reaction, resulting in improved solubility and thermal stability. The proposed method offers a green and practical solution to phosphorylate important polymers.
Article
Chemistry, Multidisciplinary
Jose Luis Serrano
Summary: Modification of unprotected nucleosides has been attracting continuous interest, with Pd-catalyzed cross-coupling reactions playing an important role, while the team's synthesis of water-soluble Pd-imidates complexes has yielded interesting results.
Article
Chemistry, Organic
Cong Jiang, Yan Zhu, Heng Li, Ping Liu, Peipei Sun
Summary: A novel electrochemical cross-coupling method was developed for the synthesis of thiocyanates and selenocyanates using readily available thiophenols or thiols with TMSCN. The protocol offers the advantages of being external oxidant-free, transition-metal-free, and operating under mild conditions, yielding moderate to high amounts of product.
JOURNAL OF ORGANIC CHEMISTRY
Article
Chemistry, Applied
Caroline Berrou, Sebastien Prevost
Summary: This study describes a direct C8-oxygenation of naphthalene derivatives using different carbonyl groups as directing groups in a palladium-catalyzed oxidation reaction with PhI(OAc)(2) in a TFA/TFAA mixture. Interestingly, the use of Weinreb amide as the directing group results in the direct formation of naphtholactone skeleton. This methodology has been successfully applied to the synthesis of variously substituted naphtholactones.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Tharique N. Ansari, Sudripet Sharma, Susanta Hazra, Frederick Hicks, David K. Leahy, Sachin Handa
Summary: A micelle-enabled catalytic carboxylation of (hetero)aryl halides has been developed, utilizing aqueous micelles to stabilize reactive carbanions and single-metal atom catalysts. Mechanistic analyses support a carbanion pathway, and the method shows broad substrate tolerance and is applied to the synthesis of isotopically enriched carboxylic acids.
Article
Chemistry, Physical
Jorge Meijide Suarez, Olivia Bistri-Aslanoff, Sylvain Roland, Matthieu Sollogoub
Summary: Encapsulation of metal centers inside cyclodextrins allows for control of coordination modes depending on cavity size and nature. The NHC ligands exhibit extraverted or introverted conformations in different sized CD cavities, influencing the behavior of metal complexes.
Review
Biochemistry & Molecular Biology
Yves Bleriot, Nicolas Auberger, Jerome Desire
Summary: Glycosidases are widespread enzymes responsible for breaking down glycoconjugates, with the potential to be inhibited for the treatment of various diseases. Efforts have been made in the past three decades to design and synthesize inhibitors, with sugars containing an amidine moiety being a focus of research.
CURRENT MEDICINAL CHEMISTRY
(2022)
Editorial Material
Chemistry, Organic
Matthieu Sollogoub
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mathieu Carlier, Emilie Lesur, Aurelie Baron, Aurelie Lemetais, Karine Guitot, Loic Roupnel, Christiane Dietrich, Gilles Doisneau, Dominique Urban, Nicolas Bayan, Jean-Marie Beau, Dominique Guianvarc'h, Boris Vauzeilles, Yann Bourdreux
Summary: Trehalose-based probes are useful tools for detecting the mycomembrane of mycobacteria through metabolic labeling. This study simplified the synthesis of trehalose analogues and demonstrated their application in one-step and two-step labeling methods for studying the mycomembrane in live mycobacteria.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
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
Thanh Van Tran, Jerome Desire, Nicolas Auberger, Yves Bleriot
Summary: A strategy for the synthesis of 1-C-phosphonomethyl and 1-C-phosphonodifluoromethyl imino-sugars is reported. The conversion of sugar lactams to imines and subsequent reactions with specific reagents leads to the formation of cis and trans-glycosyl phosphonates in moderate to good yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Lisa Tanzi, Davide Rubes, Teodora Bavaro, Matthieu Sollogoub, Massimo Serra, Yongmin Zhang, Marco Terreni
Summary: In recent years, nanomaterials based on fullerene have been regarded as promising tools for the development of efficient adjuvant/delivery systems for vaccination due to their biocompatibility, size, and easy preparation and modification. In this study, we reported the chemoenzymatic synthesis of natural polymannan analogues and their functionalization on the surface of Buckminster fullerene in a highly controlled manner. These sugar-modified derivatives showed higher yields than previous methods. The strategy was also successful in obtaining fullerene with amino acid derivatives, paving the way for the derivatization of fullerenes with immunogenic sugars and complex antigenic peptides.
Article
Chemistry, Organic
Zakaria Debbah, Jerome Marrot, Nicolas Auberger, Jerome Desire, Yves Bleriot
Summary: This article reports the synthesis of C,C-glycosides starting from 6-azidoketopyranoses. The StaudingerazaWittig-mediated cyclization and AllMgBr-mediated stereoselective opening reactions were employed to obtain beta hydroxyazepanes with a quaternary carbon alpha to the nitrogen. Aromatic rearrangement led to the formation of six-membered L-iminosugars with two functional handles at the pseudoanomeric position. The inversion of the free OH at the azepane level resulted in the formation of D-iminosugars.
Article
Chemistry, Multidisciplinary
Andrea Mascherpa, Nozomii Ishii, Ayelen Tayagui, Jiang Liu, Matthieu Sollogoub, Antony J. J. Fairbanks
Summary: Beta-cyclodextrin and its derivatives have been approved for therapeutic use in over 30 clinical settings. They show promise as therapeutics for lysosomal storage disorders and other diseases involving metabolite accumulation in the lysosome. In this study, a synthetic glycan terminated with mannose-6-phosphate residues was attached to beta-cyclodextrin and its effect on cellular internalization and transport to the lysosome was investigated.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Organic
Matthieu Sollogoub, Emmanuelle Schulz
Summary: The Division de Chimie Organique (DCO) of the Societe Chimique de France (SCF) and the European Journal of Organic Chemistry are collaborating for the second year in a row to honor the recipients of the 2021 DCO Awards.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Hugo Madec, Francisca Figueiredo, Kevin Cariou, Sylvain Roland, Matthieu Sollogoub, Gilles Gasser
Summary: The development of organometallic catalysis has expanded the toolbox of synthetic chemists and paved the way for bio-compatible reactions in water. Performing metal-catalysed reactions within living cells or organisms poses additional constraints, requiring metal complexes with good efficiency, low concentration, cell specificity, cellular uptake, and low toxicity.
Article
Chemistry, Multidisciplinary
Enxu Liu, Sawsen Cherraben, Laora Boulo, Claire Troufflard, Bernold Hasenknopf, Guillaume Vives, Matthieu Sollogoub
Summary: Researchers have developed a novel molecular information ratchet that is sensitive to both the position and orientation of a moving macrocycle. The use of a cone-shaped chiral macrocycle allows for kinetic biases, and the possibility of selective functionalization offers new opportunities in the design of molecular motors.
Article
Chemistry, Multidisciplinary
Dmitri Colesnic, Pedro J. Hernando, Lise-Marie Chamoreau, Laurent Bouteiller, Mickael Menand, Matthieu Sollogoub
Summary: Regioselective di-functionalization of a cyclodextrin enables controlled orientation of hydrophobic domains, leading to a unique hierarchical assembly in the solid state. This assembly involves synergistic host-guest inclusions, directed hydrophobic effect, and hydrogen bonding, which together create a porous organic architecture.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Jerome Desire, Zakaria Debbah, David Gueyrard, Jerome Marrot, Yves Bleriot, Atsushi Kato
Summary: A series of L-iminosugar C,C-glycosides containing an allyl group and various substituents at the pseudoanomeric position were synthesized and evaluated for their glycosidase inhibition activity. The compounds adopted a 1C4 conformation and showed weaker glycosidase inhibition compared to previously reported branched L-iminosugars. However, some compounds exhibited micromolar inhibition of human lysosome β-glucocerebrosidase, indicating their potential as potent CGase inhibitors by modifying the structure/length of the pseudoanomeric substituents.
CARBOHYDRATE RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Zhonghang Wen, Emmanuel Maisonhaute, Yongmin Zhang, Sylvain Roland, Matthieu Sollogoub
Summary: Bis-azolium salts with one azolium capping a perbenzylated alpha-cyclodextrin were used to generate Janus-type bimetallic complexes containing copper, silver, gold, or palladium salts. Encapsulation of one metal center inside the cavity allowed for control of (trans)metalation and oxidation reactions at specific positions. In particular, selective oxidation of Au-I to Au-III could be achieved outside the cavity of the cyclodextrin in the bis-Au-I Janus complex.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
