Review
Chemistry, Organic
Rodrigo Abonia, Oscar Montoya
Summary: This review examines the progress in literature on the synthesis of 1,2,2-triarylethanone derivatives from 2000 to 2020, exploring various synthetic approaches such as metal-free, metal-mediated, C-H bond activation, alpha-monoarylation, alpha,alpha-diarylation, umpolung processes, N heterocyclic carbene (NHC), and deoxygenation. Mechanistic proposals and reported data on carbon-carbon bond formation through ketone based alpha-arylation processes are also briefly discussed and organized for comparison in concise Tables/Schemes.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ji-Jia Zhou, Ya-Nan Meng, Li-Gao Liu, Yi-Xi Liu, Zhou Xu, Xin Lu, Bo Zhou, Long-Wu Ye
Summary: The functionalization of etheric C-O bonds via C-O bond cleavage is a promising method for the synthesis of C-C and C-X bonds. However, the enantioselective version of these reactions, mainly involving C(sp(3))-O bond cleavage, is highly challenging. Here, we present a copper-catalyzed asymmetric cascade cyclization, which allows for the efficient and enantioselective synthesis of chromeno[3,4-c]pyrroles with a triaryl oxa-quaternary carbon stereocenter. Notably, this protocol represents the first example of [1,2]-Stevens-type rearrangement via C(sp(2))-O bond cleavage and [1,2]-aryl migration reactions via vinyl cations.
Article
Chemistry, Multidisciplinary
Karan Goyal, Garrett A. Kukier, Xiangyang Chen, Aneta Turlik, K. N. Houk, Richmond Sarpong
Summary: A novel synthesis method for aryl-substituted, enantioenriched fulvenes from an oxidative Heck cascade and a rearrangement of a carboxy-substituted spiro[4.4]nonatriene is disclosed. Mechanistic investigations using density functional theory (DFT) calculations and empirical results show that the net transformation occurs through a Pd(ii)-mediated 1,5-vinyl shift from a vinyl-palladium intermediate, which terminates with protodepalladation. This method tolerates a range of electron-rich and deficient arylboronic acids and provides moderate to good yields and enantiomeric ratios of mono- and diaryl substituted annulated fulvenes.
Article
Electrochemistry
Yin-Long Lai, Xiao Yang, Si-Chao Wu, Xi-Yong Li, Yao-Xiong Gong, Sheng-Ling Zhang, Rui-Min Zhong, Jian-Hua Liao, Jian-Min Luo
Summary: An efficient Fe-catalyzed electrochemical synthesis method has been developed for the selective cleavage of C-O bonds in ethers under oxidant-free conditions, resulting in the synthesis of benzothiazoles. The method shows good yields and compatibility with various functional groups and has also been successfully applied to the generation of benzimidazoles and benzoxazoles.
Article
Chemistry, Physical
Yaxuan Jing, Mohsen Shakouri, Xiaohui Liu, Yongfeng Hu, Yong Guo, Yanqin Wang
Summary: Researchers have developed a strategy to selectively cleave C-C bonds in aromatic plastics using catalyst Ru/Nb2O5 through methanol poisoning, resulting in monocyclic phenolic compounds.
Article
Chemistry, Multidisciplinary
Rika Idogawa, Akihiro Kobayashi, Youngchan Kim, Ken Shimomori, Takamitsu Hosoya, Suguru Yoshida
Summary: An efficient method for sequential C-F transformations of o-hydrosilyl-substituted benzotrifluorides was developed, allowing for the synthesis of a wide variety of organofluorine compounds through successive reactions. Key to the success was the hydride reduction of o-fluorosilyl-substituted difluoromethylenes, enabling further C-F transformations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ana Amic, Dejan Milenkovic, Zoran Markovic, Denisa Cagardova, Jaime Rodriguez-Guerra Pedregal, Jasmina M. Dimitric Markovic
Summary: The kinetics and thermodynamics of phenolic O-H and C-ring C-H bond breaking in dihydrokaempferol, a natural flavonoid compound, were investigated using a density functional based approach. The study found that the 4'-OH phenolic hydrogen is involved in the inactivation of a hydroperoxyl radical (OOH), while the hydrogen atom transfer mechanism is responsible for C-H bond cleavage.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Tatsushi Yabuta, Masahiko Hayashi, Ryosuke Matsubara
Summary: The article reports a visible-light-induced photocatalytic cleavage method for alkyl aryl ether C-O bonds using a carbazole-based organic photocatalyst. Addition of Cs2CO3 is beneficial for the reaction, especially in reactions using a N-H carbazole organic photocatalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Physical
Hao Zhou, Yaxuan Jing, Yanqin Wang
Summary: This article discusses the importance of sustainable fuels and chemicals in achieving global carbon neutrality. It focuses on the catalytic activation and cleavage of C-O/C-C bonds in biomass conversion, highlighting the challenges and possible strategies using cooperative catalysis. The article mainly discusses the activation and cleavage of C-O bonds and the cleavage of C-C bonds in carbohydrates and lignin, offering insights and future directions for research in this field.
ACTA PHYSICO-CHIMICA SINICA
(2022)
Article
Chemistry, Multidisciplinary
Mo Zhang, Zheng Li, Yeqin Feng, Xing Xin, Guo-Yu Yang, Hongjin Lv
Summary: Selective photocatalytic hydrogenolysis of lignin beta-O-4 models was achieved using Ni-containing polyoxometalate (POM) catalysts and CdS quantum dots under blue LED light irradiation. The system demonstrated high conversion and selectivity in transforming lignin beta-O-4 models to phenols and ketones. A potential photocatalytic mechanism was proposed based on experimental and spectroscopic analyses. This facile strategy has the potential for the photocatalytic production of various value-added chemicals from natural or biomass derivatives.
Article
Chemistry, Multidisciplinary
Christopher E. Rivas, Jose C. Alvarado-Monzon, Gerardo Gonzalez-Garcia, J. Oscar C. Jimenez-Halla, Jesus Rangel-Garcia, Crispin Cristobal, Jorge A. Lopez
Summary: The study presents the synthesis of complexes 1 and 2 through oxidative coordination and cleavage of C-3-C(O)Me bond of L1. Plausible mechanisms for the reactions leading to the formation of complexes 1 and 2 are proposed using DFT calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Julia Soika, Calum McLaughlin, Tomas Nevesely, Constantin G. Daniliuc, John. J. Molloy, Ryan Gilmour
Summary: This study presents a mild organophotocatalytic N-O bond cleavage method that allows for the cleavage of bonds without harsh conditions. The method demonstrates synthetic utility for a broad range of compounds and enables the synthesis of ambiphilic amide aldehydes with varying chain lengths.
Article
Chemistry, Organic
Chae Yeon Lee, Su Eun Lee, Hee Nam Lim
Summary: An SN1-type fluorination method for monofluoroethers is developed using oxygen-assisted Beckmann fragmentation to drive fluorinative C-C bond cleavage. Cyclic a-aryloxyoximes derived from 3-coumaranone and 1-indanones were investigated as substrates, with N,N-diethylamino-sulfur trifluoride (DAST) acting as a dual-role reagent of an oxime activator and fluoride donor. This method allows for the synthesis of an underdeveloped chemical motif under simple and mild operating conditions.
Article
Chemistry, Physical
Chun Gu, Weiqiang Yu, Hanqing Zhao, Song Shi, Penghua Che, Jie Xu, Jin Gao
Summary: Ru/porous silica regulated by templates with different carbon chain lengths exhibit the ability to control the methane yield in biomass polyols hydrogenolysis.
Article
Chemistry, Physical
Adrian Luguera Ruiz, Marta La Mantia, Daniele Merli, Stefano Protti, Maurizio Fagnoni
Summary: This study addresses the urgent need for developing uncharged radical precursors activated under mild photocatalyzed conditions, utilizing 2-substituted-1,3-oxazolidines to release various radicals and achieve unprecedented C-C bond cleavage, enabling light-driven radical addition reactions.
Article
Biochemistry & Molecular Biology
Florent Kerdraon, Gemma Bogard, Benoit Snella, Herve Drobecq, Muriel Pichavant, Vangelis Agouridas, Oleg Melnyk
Summary: Thiol-based catalysts are commonly used for chemical protein synthesis, but the development of selenol-based catalysts is still in its early stages. This study compared different selenols for their ability to promote thiol-thioester exchanges and demonstrated the successful total synthesis of a biologically active human chemotactic protein using a selected selenol compound.
Article
Chemistry, Multidisciplinary
Vincent Diemer, Olga Firstova, Vangelis Agouridas, Oleg Melnyk
Summary: This article presents the fundamental principles and factors affecting the rate of native chemical ligation, as well as how to control it. It serves as a quick guide for finding an appropriate catalyst.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Benoit Snella, Benjamin Grain, Jerome Vicogne, Frederic Capet, Birgit Wiltschi, Oleg Melnyk, Vangelis Agouridas
Summary: Latent oxalyl thioester surrogates are a powerful tool for modifying peptides and proteins in diluted conditions. They are designed to be stable and can be activated on demand for ligation reactions with peptide concentrations as low as a few hundred nM at high rates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Vangelis Agouridas, Nathalie Ollivier, Jerome Vicogne, Vincent Diemer, Oleg Melnyk
Summary: The last two decades have witnessed the rise in power of chemical protein synthesis, which now constitutes an established corpus of synthetic methods effectively complementing biological approaches. The emergence of chemoselective reactions enabling the formation of native peptide bonds between unprotected peptidic segments has contributed to this evolution. These native ligation reactions have fueled the production of homogeneous batches of large and highly decorated protein targets and have found successful applications in various fields such as chemical biology, medicinal chemistry, materials science, and nanotechnology research.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Editorial Material
Chemistry, Multidisciplinary
Vincent Diemer, Oleg Melnyk
Summary: The development of powerful one-pot techniques combining native chemical ligation and cysteine reductive desulfurization is crucial for protein production by chemical synthesis. In the September issue of Chem, Xuechen Li and colleagues achieved this goal by combining sodium tetraethylborate and a phosphine as a post-ligation treatment.
Article
Multidisciplinary Sciences
Nathalie Ollivier, Magalie Senechal, Remi Desmet, Benoit Snella, Vangelis Agouridas, Oleg Melnyk
Summary: Phosphorylation is a mechanism used by cells to promote protein-biomolecule association. In this study, the authors demonstrate the effects of interactions between proteins equipped with positively charged arginines and peptides harboring negatively charged phosphoserines, enabling rate acceleration and chemical processes under dilute conditions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Remi Desmet, Celine Boidin-Wichlacz, Reda Mhidia, Aurelie Tasiemski, Vangelis Agouridas, Oleg Melnyk
Summary: One pillar of protein chemical synthesis is the selective desulfurization of cysteine residues into alanines, using ligation chemistries based on reactions involving phosphine as a sink for sulfur. This study demonstrates that cysteine desulfurization by a phosphine can be efficiently achieved using micromolar concentrations of iron under aerobic conditions in hydrogen carbonate buffer, reminiscent of iron-catalyzed oxidation phenomena occurring in natural waters. Therefore, this work highlights the potential of adapting chemical processes in aquatic systems for chemoselective transformations at the protein level, while minimizing the use of harmful chemicals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Nathalie Ollivier, Eliott Roy, Vangelis Agouridas, Vincent Diemer, Oleg Melnyk
Summary: 4-Mercaptophenylacetic acid (MPAA) is a commonly used catalyst for native chemical ligation (NCL), but it requires a large excess for practical rates (up to 50-100 equivalents). In this study, we found that the catalytic potency of MPAA can be enhanced by introducing a stretch of arginines in the departing thiol of the thioester. This electrostatically assisted NCL reaction allows for rapid synthesis using substoichiometric concentrations of MPAA, which is advantageous for practical applications.
Article
Chemistry, Organic
Benjamin Grain, Remi Desmet, Benoit Snella, Oleg Melnyk, Vangelis Agouridas
Summary: In this study, a latent and highly reactive oxalyl thioester precursor was efficiently introduced into a fully synthetic protein domain, serving as an on-demand reactive handle. This approach has potential applications in life or materials sciences.
Meeting Abstract
Biochemistry & Molecular Biology
Vangelis Agouridas, Ouafaa El Mahdi, Oleg Melnyk
JOURNAL OF PEPTIDE SCIENCE
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Vangelis Agouridas, Benoit Snella, Grain Benjamin, Jerome Vicogne, Birgit Wiltschi, Oleg Melnyk
JOURNAL OF PEPTIDE SCIENCE
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Vincent Diemer, Olga Firstova, Vangelis Agouridas, Oleg Melnyk
JOURNAL OF PEPTIDE SCIENCE
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Florent Kerdraon, Benoit Snella, Vangelis Agouridas, Vincent Diemer, Oleg Melnyk
JOURNAL OF PEPTIDE SCIENCE
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Oleg Melnyk, Nathalie Ollivier, Magalie Senechal, Remi Desmet, Benoit Snella, Vangelis Agouridas
JOURNAL OF PEPTIDE SCIENCE
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Nathalie Ollivier, Magalie Senechal, Remi Desmet, Herve Drobecq, Vangelis Agouridas, Oleg Melnyk
JOURNAL OF PEPTIDE SCIENCE
(2022)
