Article
Chemistry, Multidisciplinary
Merlin Hess, Ivo Krummenacher, Theresa Dellermann, Holger Braunschweig
Summary: A series of highly substituted 1,2-azaborinines, including a phenylene-bridged bis-1,2-azaborinine, was successfully synthesized in this study. The new method using rhodacycles instead of 1,2-azaborete complexes as precursors proved to be more effective in the synthesis of a wider range of 1,2-azaborinines.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Raffaella Mancuso, Patrizio Russo, Melania Lettieri, Domenico Santandrea, Corrado Cuocci, Bartolo Gabriele
Summary: Polycyclic heterocyclic derivatives can be synthesized in one step by a carbonylative double cyclization approach, with yields ranging from 45% to 86%, showing promising potential for various applications.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ze-Jie Lv, Wei Liu, Wen-Xiong Zhang
Summary: As key intermediates in metal-promoted/catalyzed C-C bond coupling reactions of nitriles and alkynes, azametallacyclopentadienes, M(N=CR1-CR2=CR3), are an important class of azametallacycles. Research on their solid-state structures, intrinsic reactivity, and synthetic application was limited until the beginning of this century when they were found to have applications in the synthesis of heterocycles. Since then, various complexes with this motif have been isolated and characterized, including rare-earth azametallacyclopentadienes which show high reactivity towards unsaturated molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Bartosz Bisek, Wojciech Chaladaj
Summary: This study describes the Pd-catalyzed tandem cyclization/coupling of internal β-propargylic β-ketoesters with (hetero)aryl bromides. Two protocols are established to selectively produce either 2-benzylidene-dihydrofurans or 2-benzyl-furans. The proposed catalytic cycle involves oxidative addition, substitution of bromide with alkyne, rate-limiting anti-selective 5-exo-dig oxocyclization, deprotonation of the oxonium intermediate, and reductive elimination.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ramon Arora, Jose F. Rodriguez, Andrew Whyte, Mark Lautens
Summary: A palladium-catalyzed strategy has been proposed for synthesizing unsymmetrically linked heterocycles within stereoselective tetrasubstituted olefins, with high yields and excellent stereoselectivities achieved using low catalyst loadings. Mechanistic studies suggest a syn-carbopalladation of the carbamoyl chloride followed by Pd-II-catalyzed cyclization of alkyne-tethered nucleophiles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Raffaella Mancuso, Alex De Salvo, Patrizio Russo, Aurelia Falcicchio, Nicola Della Ca, Leonardo Pantoja Munoz, Bartolo Gabriele
Summary: The PdI2/KI-catalyzed oxidative carbonylation of 4-(2-aminophenyl)-3-yn-1-ols selectively produces dihydrofuroquinolinone derivatives in fair to high yields (60%-89%) and excellent turnover numbers (180-267 mol of product per mol of Pd) over 19 examples. This reaction involves the catalytic construction of two rings and three new bonds in one step, providing high value added fused heterocyclic structures from readily available materials.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Shuai Jiang, Wen-Bin Cao, Xiao-Ping Xu, Shun-Jun Ji
Summary: A Co-catalyzed cyclization reaction of isocyanides, azides, and amines was developed to access quinazoline derivatives, featuring high atom economy, mild reaction conditions, excellent yields, and a broad substrate scope. The cascade reaction involved the formation of three to four C-N bonds and one or two rings, producing versatile intermediates for further transformations. The cobalt catalyst used in the reaction was found to be isolatable and reusable.
Article
Chemistry, Physical
Jian-Shu Wang, Jiangjie Zhang, Siqi Wang, Jun Ying, Chuan-Ying Li, Xiao-Feng Wu
Summary: A novel palladium-catalyzed domino carbonylative cyclization has been developed for the rapid construction of functionalized heterocycles. The reaction proceeds smoothly with the consecutive formation of C-C and C-X bonds using benzene-1,3,5-triyl triformate as the CO source, yielding a variety of biologically relevant derivatives.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Applied
Raffaella Mancuso, Patrizio Russo, Rossana Milie, Marzia Dell'Aera, Fedora Grande, Nicola Della Ca
Summary: A Pd-catalyzed carbonylative double cyclization approach to a novel class of S,O-bicyclic heterocycles is presented, allowing the construction of previously unreported compounds with high yields.
Article
Chemistry, Multidisciplinary
Franziska Spruner von Mertz, Ricardo Molenda, Sebastian Boldt, Alexander Villinger, Peter Ehlers, Peter Langer
Summary: A series of previously unknown 5,14-diphenylbenzo[j]naphtho[2,1,8-def][2,7]phenanthrolines, incorporating a 5-azatetracene and a 2-azapyrene subunit, were successfully synthesized using Pd-catalyzed cross-coupling reactions and a one-pot Povarov/cycloisomerization reaction. This synthetic approach enables extensive diversification of the heterocyclic core structure. The optical and electrochemical properties of these compounds were investigated through experimental and computational studies, revealing their closer electronic and optical resemblance to 2-azapyrenes rather than the typical characteristics of 5-azatetracene moieties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Arpad Molnar
Summary: This review aims to analyze recent studies on the synthesis of five-membered nitrogen heterocycles using palladium catalysts. The focus is on studies from the last three years. The common feature of these methods is the formation of nitrogen-containing five-membered rings through the ring closing of appropriate starting materials. The selected examples demonstrate that a wide range of products, from small monocycles to condensed multi-ring systems, can be efficiently obtained with high yields and stereoselectivities under mild reaction conditions.
Article
Chemistry, Multidisciplinary
Sanghyup Seo, Donghyeon Kim, Hyunwoo Kim
Summary: The reductive cross-coupling of terminal alkenes and N-heterocyclic bromides was successfully demonstrated through ligand optimization of Pd and CuH catalysis. The optimized ligands for Pd and CuH catalysis, Briphos and DTB-DPPBz respectively, were further applied to gram-scale production of clathryimine B.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Suchen Zou, Zeyu Zhao, Hanmin Huang
Summary: In this study, a novel and efficient palladium-catalyzed reaction was developed for the regioselective and stereodivergent ring-closing of aminoenynes with aldehydes and boronic acids or hydrosilane. The reaction allows for the synthesis of a series of exocyclic 1,3-dienes bearing saturated N-heterocycles of 5- to 8-membered rings. It utilizes a simple Pd-catalyst and works under mild reaction conditions with a broad range of substrates. The resulting products serve as useful intermediates for chemical synthesis due to the versatility of the conjugated diene. Preliminary mechanistic details of the reaction are also uncovered.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Quentin Dherbassy, Srimanta Manna, Chunling Shi, Watcharapon Prasitwatcharakorn, Giacomo E. M. Crisenza, Gregory J. P. Perry, David J. Procter
Summary: In this study, an enantioselective copper-catalyzed borylative cyclization was reported for the assembly of privileged pyrroloquinazolinone motifs. The reaction demonstrated high enantio- and diastereocontrol, yielding products with quaternary stereocenters. The utility of the products was further demonstrated through additional manipulations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Sami Chniti, Laszlo Kollar, Attila Benyei, Agnes Dornyei, Attila Takacs
Summary: Novel N-substituted pyrrolo[3,4-b]quinoline-1,3-diones have been synthesized successfully through a highly selective palladium-catalyzed carbonylative imidazation-cyclization reaction. This method, applied for the first time to access original scaffolds, involves 3-bromo-2-iodoquinoline as a typical partner, primary amines, and atmospheric or high carbon monoxide pressure. The use of bidentate ligands such as XantPhos and dppp in atmospheric or high-pressure conditions provides a wide range of carbonylated compounds with good to excellent yields (up to 82%). Furthermore, new quinoline-2,3-dicarboxamides have been isolated as side products in very low yields and have been fully characterized. The solid state structures of three synthesized acridinimides have been unequivocally established by single-crystal XRD analysis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wanjun Zhu, Qikai Sun, Hai Chang, Hui-Xing Zhang, Quanquan Wang, Gong Chen, Gang He
Summary: A new protocol for the synthesis of 2-deoxy-C-aryl-glycosides and 2-deoxy-C-alkyl-glycosides via iridium-catalyzed directed C-H glycosylation with glycals is reported. The benzoxazole directing group can be cleanly removed by the treatment of KOH or LiAlH4, offering a versatile method for the synthesis of these glycosides.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Xin Chu, Linhua Shen, Bo Li, Peng Yang, Chengzhuo Du, Xiaoye Wang, Gang He, Samir Messaoudi, Gong Chen
Summary: A simple and versatile method has been developed for macrocyclizing unprotected native peptides using a wide range of easily accessible diiodo and triiodoarene reagents via palladium-catalyzed multiple S-arylation of cysteine residues. This method allows for the incorporation of iodoarenes with different cores into peptide macrocycles of varied ring sizes and amino acid compositions with high efficiency and selectivity under mild conditions.
Article
Multidisciplinary Sciences
Bo Li, Lan Wang, Xiangxiang Chen, Xin Chu, Hong Tang, Jie Zhang, Gang He, Li Li, Gong Chen
Summary: In this study, a method for macrocyclization of two free-amine-containing residues in mild conditions is disclosed. This method can efficiently generate complex peptide structures, expanding the toolbox for peptide chemistry.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Peng Yang, Chao Zhang, Bo Li, Gang He, Gong Chen
Summary: A new protocol for the synthesis of thioether-linked peptide macrocycles has been developed, using PEGA resin and a mixed solvent of CH3CN and H2O. This method allows for the preparation of peptide macrocycles of varied ring size, composition, and with different thioether linkers in moderate to good yield with one column chromatography purification.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shaokun Cai, Qikai Sun, Quanquan Wang, Gang He, Gong Chen
Summary: Metal-catalyzed C-H glycosylation reactions are important strategies for the synthesis of C-glycosides. This study developed a new ruthenium catalyst for the ortho C-H glycosylation of arenes with various glycosyl chloride donors using a monodentate pyridine directing group.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Ziqian Bai, Shiyang Zhu, Yiyao Hu, Peng Yang, Xin Chu, Gang He, Hao Wang, Gong Chen
Summary: This study reports a method for the synthesis of N-acyl sulfenamides via copper-catalyzed S-amidation of thiols with dioxazolones. This method is efficient, convenient, and broadly applicable. The resulting N-acetyl sulfenamides can be used as highly effective S-sulfenylation reagents and enable the synthesis of sterically demanding disulfides that are difficult to prepare by other means.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xin Chu, Bo Li, Hao-Yang Liu, Xiaowei Sun, Xiaochen Yang, Gang He, Chuanzheng Zhou, Weimin Xuan, Shu-Lin Liu, Gong Chen
Summary: In this study, a simple and powerful method for bioconjugation is reported, using ortho-phthalaldehyde (OPA) reagent to efficiently and selectively crosslink various alpha-amino acids, aryl amines, and secondary amines to the epsilon-amino side chain of lysine on peptides or proteins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yaxin Wang, Zehui Cao, Qin He, Xin Huang, Jiaxi Liu, Helfried Neumann, Gong Chen, Matthias Beller
Summary: A simple and efficient method has been developed for activating perfluoroalkyl iodides using tBuONa or KOH, without the need for expensive photo- or transition metal catalysts. This method enables various transformations including alpha-sp(3) C-H amidation reactions of alkyl ethers and benzylic hydrocarbons, C-H iodination of heteroaryl compounds, and perfluoroalkylations of electron-rich pi bonds. Mechanistic studies have shown that these reactions are mediated by halogen bond interactions between perfluoroalkyl iodides and tBuONa or KOH, leading to the homolysis of perfluoroalkyl iodides under mild conditions.
Article
Chemistry, Multidisciplinary
Peng Yang, Martynas J. Sirvinskas, Bo Li, Nicholas W. Heller, Hua Rong, Gang He, Andrei K. Yudin, Gong Chen
Summary: In this study, a broadly applicable strategy to remodel the structure of homodetic peptides by cross-linking the aromatic side chains of Trp, His, and Tyr residues with various aryl linkers is reported. The aryl linkers can be easily installed via copper-catalyzed double heteroatom-arylation reactions of peptides with aryl diiodides. These aromatic side chains and aryl linkers can be combined to form a large variety of assemblies of heteroatom-linked multi-aryl units. The assemblies can serve as tension-bearable multi-joint braces to modulate the backbone conformation of peptides as an entry to previously inaccessible conformational space.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Qin He, Zehui Cao, Yangyang Zhang, Gong Chen, Yaxin Wang
Summary: A novel radical reaction system mediated by azidobenziodoxole (BIN3) was developed for selective chlorination and bromination of tertiary and secondary C(sp(3)) H bonds of alkyl substrates using haloform as the halogen donor. The reactions of various substrates with BIN3 under visible light irradiation yielded C-H chlorinated or brominated products without the need for any photo or metal catalysts. The mechanism involves haloform serving as the halogen atom donor and HN3 generated in situ from the reaction of BIN3 and water as the hydrogen atom donor, which propagate a radical chain reaction by abstracting a hydrogen atom from the alkane substrate.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Yifei Zhou, Hongjun Li, Yi Huang, Jiahui Li, Guiyu Deng, Gong Chen, Zhen Xi, Chuanzheng Zhou
Summary: During solid-phase peptide synthesis (SPPS), the main side reactions of protected amino acids are hard to remove. The authors here report a thiol-labile amino protecting group, DNPBS, which greatly suppresses these side reactions observed in conventional SPPS. Although DNPBS SPPS is less efficient than Fmoc SPPS, they can be combined to synthesize peptides that are otherwise difficult to obtain.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Shi-Yang Zhu, Wen-Ji He, Guan-Chi Shen, Zi-Qian Bai, Fang-Fang Song, Gang He, Hao Wang, Gong Chen
Summary: In this work, we demonstrate that bulky alkylphosphines such as PtBu3 can switch from being active ligands to being spectator ligands, promoting the FeCl2-catalyzed N-amidation reaction of arylamines with dioxazolones to yield hydrazides with high efficiency and chemoselectivity. Mechanistic studies show that the phosphine ligands can enhance the decarboxylation of dioxazolones on the iron center, and hydrogen bonding interactions between the arylamines and the ligands on Fe nitrenoid intermediates might play a role in tuning the delicate interplay between phosphine ligand, arylamine, and acyl nitrene N, thereby favoring N-N coupling over N-P coupling. The ligand-promoted N-amidation protocols presented here provide a convenient approach to access various challenging triazane compounds through double or sequential N-amidation of primary arylamines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yaxin Wang, Qin He, Zehui Cao, Peng Wang, Gong Chen, Matthias Beller
Summary: This study reports a visible-light-promoted and radical-mediated strategy for the site-specific cleavage of C(sp(3))-C(sp(3)) bonds in ethers. Different cyclic and linear alkyl ethers can be converted into benzoylated acetals and aldehydes or ketones under mild conditions in the presence of Ru(bpy)(3)Cl-2 as a photocatalyst and Zhdankin's lambda(3)-azidoiodane reagent, with moderate to high yields. Control experiments and mechanistic investigations provide a plausible mechanism for this unusual deconstructive esterification of ethers.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Peng Yang, Xuan Wang, Bo Li, Yixuan Yang, Jinfeng Yue, Yanrui Suo, Huarong Tong, Gang He, Xiaojie Lu, Gong Chen
Summary: A highly efficient method for constructing peptide macrocycles has been developed through palladium-catalyzed S-arylation of alkyl and aryl thiols with aryl iodides. This method allows for the assembly of peptide macrocycles of various sizes and compositions in high yield. Screening of an 8-million-membered tetrameric cyclic peptide DNA-encoded library identified compounds with single digit micromolar inhibition activity against protein p300.
Article
Chemistry, Multidisciplinary
Bo Li, Jie Zhang, Li Li, Gong Chen
Summary: A practical method for chiroptical sensing of free alpha amino acids has been developed, utilizing a three-component labeling reaction to derivatize analytes into an isoindole for sensitive CD and UV readouts. The assay shows high selectivity and accuracy across a wide range of concentrations, with a unprecedented lower limit of 10 micromolar concentration.
