Article
Chemistry, Multidisciplinary
Huijun Qian, Hieu D. Nguyen, Leiyang Lv, Shuming Chen, Zhiping Li
Summary: The study developed an efficient method to incorporate the hydrazone moiety into the products through palladium/NHC-catalyzed fluoroallylation/annulation of gem-difluorocyclopropanes (gem-F(2)CPs) with hydrazones. Thermodynamically unstable fluorinated E-allylation products were obtained with aryl ketone hydrazones, while monofluorinated products with branched selectivity were obtained with di-alkyl ketone hydrazones. Two kinds of pyrazoles were obtained via a defluorinative allylation/annulation cascade with aldehyde hydrazones, and different carbon atoms of gem-F(2)CPs could be incorporated into the pyrazole rings regiospecifically. DFT calculations revealed that the divergent selectivity was kinetically controlled and the final C-C bond formation proceeded through a 7-membered TS.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hao Wang, Hoimin Jung, Fangfang Song, Shiyang Zhu, Ziqian Bai, Danye Chen, Gang He, Sukbok Chang, Gong Chen
Summary: N-N linkages are important in natural compounds, and a nitrene-mediated intermolecular N-N coupling reaction using iridium or iron catalysis provides a simple and efficient method to synthesize various hydrazides from readily available carboxylic acid and amine precursors. Mechanistic studies show that the nitrogen atom of Ir acyl nitrene intermediates serves as a strong electrophile and can form N-N bonds with high efficiency and chemoselectivity with the assistance of Cl···HN hydrogen bonding.
Article
Chemistry, Organic
Weiyu Li, Xiaofei Chen, Lei Zhou
Summary: A photocatalytic three-component reaction was developed for the synthesis of gem-difluoroalkenes. The strong electron-withdrawing nature of the sulfonyl group enables the conversion of gem-difluoroalkenes into various monofluorocyclo-pentenes in one pot through intramolecular base-mediated SNV reactions.
Article
Biochemistry & Molecular Biology
Hongfei Wu, Xingxing Lu, Jingbo Xu, Xiaoming Zhang, Zhinian Li, Xinling Yang, Yun Ling
Summary: A series of new N-(thiophen-2-yl) nicotinamide derivatives were designed and synthesized based on the modification of natural products and the active substructure splicing method. Among them, compounds 4a and 4f showed excellent fungicidal activities and had higher control efficacies compared to commercial fungicides. These derivatives are significant lead compounds, and compound 4f is a promising fungicide candidate.
Article
Chemistry, Multidisciplinary
Jianbo Liu, Matthew F. L. Parker, Sinan Wang, Robert R. Flavell, F. Dean Toste, David M. Wilson
Summary: The synthesis of N-trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature has been reported. This method desulfurizes isothiocyanates with AgF and then acylates the formed derivative to afford N-trifluoromethyl amides, including previously inaccessible structures. The strategy provides a platform for rapidly generating N-trifluoromethyl amides by virtue of the diversity and availability of both reaction partners and could find application in the modification of advanced intermediates.
Article
Chemistry, Organic
Liubov I. Panferova, Mikhail O. Zubkov, Mikhail D. Kosobokov, Alexander D. Dilman
Summary: This study presents the removal of a tetrafluoropyridinyl group tethered to a sulfur atom using a complex of N-heterocyclic carbene (NHC) with borane. The reaction is carried out under blue light irradiation with a disulfide as a radical initiator. Selective cleavage of S-Ar bond rather than the weaker S-Alk bond is achieved through aromatic radical substitution of the thiyl group by a NHC-stabilized boron-centered radical. Alkyl thiols, the primary products of dearylation, can be in situ oxidized or alkylated to form disulfides or sulfides, respectively.
Article
Chemistry, Analytical
Canwei Peng, Longsheng Pei, Shouhui Chen, Yonghai Song, Li Wang
Summary: In this work, a hydrazone-linked covalent organic framework (COF) with abundant N and O atoms was prepared for sensitive detection of heavy metal ions (HMIs). The hydrazone-linked TP-TD COF showed three-dimensional network morphology, improved crystallinity and chemical stability. The COF could promote the migration of HMIs and utilized the affinity of N and O atoms to detect HMIs.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Applied
Jieming Zhang, Zhan-Ming Zhang, Qi Wu, Junliang Zhang
Summary: A Pd-catalyzed synthesis method for 1,2,3,4-tetrahydroisoquinoline (THIQ) was developed, involving oxidative addition, carbene insertion, and cyclization steps.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Aamer Saeed, Saba Ashraf, Ghulam Shabir, Tuncer Hokelek, Ulrich Floerke, Asma Mukhtar, Muhammad Saeed
Summary: The N- (diethylcarbamothioyl)furan-2-carboxamide (3) was successfully synthesized in excellent yield and purity. The crystal structure analysis confirmed the coplanarity of the furan ring and aminocarbamothioyl moiety in 3, as well as the presence of an intramolecular hydrogen bond. The study also investigated the intermolecular interactions in the crystal packing and determined the electrochemical properties of 3 using ab initio and density functional models.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Organic
Athira Parammal, Shubham Singh, Manoj Kumar, Joe Sam Xavier, Parthasarathi Subramanian
Summary: In this study, we report the first Mn(I)-catalyzed C(sp(2))-H chemoselective in situ dienylation and diastereoselective intramolecular Diels-Alder reaction using iso-pentadienyl carbonate to access 6/6/5-fused tricyclic scaffolds. Extensive mechanistic studies have supported the proposed mechanism of this cascade reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Guillaume Laconde, Muriel Amblard, Jean Martinez
Summary: A simple method for synthesizing α-amino acid N-carboxyanhydrides (NCAs) without using phosgene and halogen is described. The process is safe, easy to operate, and does not require special installation, generating nontoxic, easy to remove byproducts. It is suitable for on-demand on-site production of NCAs in small or large quantities.
Article
Plant Sciences
Oriel A. Sanchez-Velasco, Jorge Saavedra-Olavarria, Daniel A. A. Araya-Santelices, Patricio Hermosilla-Ibanez, Bruce K. Cassels, Edwin G. Perez
Summary: A practical methodology to obtain rare N-Arylcytisine derivatives was reported, utilizing the copper-catalyzed Chan-Lam coupling. The study demonstrated the versatility of the Chan-Lam cross-coupling reaction in the derivatization of natural products.
JOURNAL OF NATURAL PRODUCTS
(2021)
Article
Chemistry, Organic
Yongchan Jian, Fei Wen, Jianping Shang, Xiaolong Li, Zhenyu Liu, Yuanyuan An, Yubin Wang
Summary: A photocatalysed dearomative beta-hydroborylation reaction of indole derivatives with NHC-boranes was developed for the construction of borylated indolines, which are important structural units in pharmaceuticals, natural products and functional materials.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Kuga Arima, Satoko Akiyama, Kazuo Shin-ya, Kenichi Matsuda, Toshiyuki Wakimoto
Summary: Heterocycles with N-N bonds are important components of synthetic drugs and natural products, but their biosynthetic logic is poorly understood. Through gene knockouts and biochemical experiments, we have revealed the major steps in actinopyridazinone biosynthesis, including the unprecedented mechanism involving carrier protein-mediated dihydropyridazinone formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Biochemistry & Molecular Biology
Sofie Dekimpe, Joleen Masschelein
Summary: Nonribosomal peptide synthetases are molecular machines that produce structurally complex peptide natural products with applications in medicine and agriculture. The condensation domains in these synthetases play a central role in catalyzing amide bond formation and have been shown to have diverse functions beyond conventional peptide bond formation.
NATURAL PRODUCT REPORTS
(2021)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.