Article
Chemistry, Organic
Anastasiya Fedinchyk, Maksym Herasymchuk, Vladyslav O. Smirnov, Kostiantyn P. Melnykov, Dmytro Yarmoliuk, Andrii A. Kyrylchuk, Oleksandr O. Grygorenko
Summary: Efficient approaches for the synthesis of fluorinated pyrazoles and pyrimidines with saturated (hetero)cyclic substituents were described. The methods rely on heterocyclizations using sp(3)-enriched beta-bromo-alpha,alpha-difluoroketones and fluorinated enaminones derived from saturated heterocyclic alpha-fluoroketones. These compounds serve as useful synthetic intermediates and meet the lead-oriented synthesis criteria.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jie Wang, Shan-Shan Wang, Jun Xiao, Yu-Jie He, Xin-Yan Wu, Xingguang Li, Pei-Nian Liu
Summary: CF3-substituted imidoyl sulfoxonium ylides (TFISYs) are versatile and powerful synthons for the synthesis of diverse CF3-substituted N-heterocycles, offering broad application prospects.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Bingbin Zhu, Hang Han, Wei-Ke Su, Boan Yan, Zhi Li, Chuanming Yu, Xinpeng Jiang
Summary: A metal-free intramolecular carbofluorination protocol for the synthesis of tetrasubstituted monofluoroalkenes from internal alpha,beta-ynones and Selectfluor is reported, demonstrating high stereoselectivity and broad functional group tolerance. Chelation between tetrafluoroborate anion and the aldehyde group oxygen enhances stereoselectivity, with tetrafluoroborate serving as the direct fluorine source. Furthermore, the addition of sodium tetrafluoroborate allows for multiple reuse of Selectfluor without loss of reactivity.
Article
Chemistry, Organic
Xiaoxiang Zhang, Yingying Zhang, Xiaoting Gu, Zhuan Zhang, Wanxing Wei, Taoyuan Liang
Summary: A copper-mediated 2,3-difunctionalization of indoles to afford 3-halogenated 2,3 '-biindoles is described. The protocol uses readily available feedstocks and a naturally abundant copper catalyst system, which allows the regioselective formation of C-C and C-X (X = Cl & Br) bonds in one single operation. Copper metal salt serves not only as a catalyst but also as a reactant to provide the source of halogen, avoiding the use of environmentally unfriendly reagents and displaying good functional group compatibility.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Siyu Pan, Mengshi Song, Lingling Zuo, Xiao Geng, Lei Wang
Summary: In this study, a practical strategy is presented for the direct construction of structurally diverse trifluoromethyl carbinol-containing compounds, specifically CF3-substituted tertiary alcohols with chromone derivatives. These compounds are synthesized from easily available o-hydroxyaryl enaminones and trifluoroacetaldehyde/ketone derivatives under metal-free conditions. The reaction exhibits a broad substrate scope with good yields and easy scalability. Additionally, a one-pot, two-step reaction of the obtained products with amidines is developed to produce a series of multi-substituted pyrimidine derivatives bearing two unique hydroxyls and one trifluoromethyl functional unit.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Joel Haefliger, Olga O. Sokolova, Madina Lenz, Constantin G. Daniliuc, Ryan Gilmour
Summary: The success of saturated, fluorinated heterocycles in drug discovery has led to increased research efforts in main group catalysis. By utilizing iodine(I)/iodine(III) catalysis, selective fluorinated analogs with stereocontrol have been synthesized. Furthermore, the key stereoelectronic interactions in the products have been confirmed through X-ray crystal structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Thikhamporn Uppalabat, Nattawoot Hassa, Natthapat Sawektreeratana, Pawaret Leowanawat, Pattarapapa Janthakit, Phattananawee Nalaoh, Vinich Promarak, Darunee Soorukram, Vichai Reutrakul, Chutima Kuhakarn
Summary: This study investigates the persulfate-promoted radical cascade trifluoromethylthiolation and cyclization of 3-alkyl-1-(2-(alkynyl)phenyl)indoles with AgSCF3. The protocol offers a new route to CF3S-substituted indolo[1,2-a]quinoline-7-carbaldehydes and CF3S-substituted indolo[1,2-a]quinoline-7-methanone derivatives through the formation of C-SCF3 and C-C bonds, as well as benzylic carbon oxidation in a single step. The reaction is compatible with a wide range of functional groups. The chemical structure of the product is confirmed by single-crystal X-ray diffraction data.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Lin Wang, Shengyang Ni, Josep Cornella
Summary: This manuscript describes the oxidative fluorination of aryl phosphorothiolates to access Ar-SF4Cl compounds, which are precursors for the highly coveted Ar-SF5 compounds. The protocol has been demonstrated for >10 examples and showed good tolerance to various functional groups. Additionally, AgBF4 was shown to be an effective fluorinating agent for yielding Ar-SF5 compounds.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Max Wienhold, John J. Molloy, Constantin G. Daniliuc, Ryan Gilmour
Summary: Modular beta-borylacrylates have been shown to play a crucial role in generating diverse coumarins, with the BPin unit enabling the cascade annulation of 2-halo-phenol derivatives. Mild isomerisation allows for the synthesis of structurally varied coumarins, and the method has potential applications in bioassay development and drug repurposing.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Marc Devillard, Nour Nour Eddine, Marie Cordier, Gilles Alcaraz
Summary: A straightforward synthetic methodology for the preparation of photochromic siloles based on the dithienylethene motif has been developed. This method relies on an efficient palladium-catalyzed annulation reaction of a 2,3-bis(3-thienyl)-silirene with terminal alkynes in mild conditions. The reaction is functional group-tolerant and can be extended to the synthesis of photochromic polymers with different degrees of photochromic unit incorporation by adjusting the polymer/silirene stoichiometric ratio.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Philip R. D. Murray, Isabelle Nathalie-Marie Leibler, Sandrine M. Hell, Eris Villalona, Abigail G. Doyle, Robert R. Knowles
Summary: We introduce a two-component annulation strategy that involves the combination of aryl alkenes and redox-active radical precursors bearing tethered nucleophiles, enabling the synthesis of a diverse collection of five- and six-membered saturated heterocycles. This strategy employs an Ir(III) photocatalyst and a Bronsted acid under visible-light irradiation. The synthesis involves reductive proton-coupled electron transfer, radical addition to alkene, oxidative radical-polar crossover, and cyclization of the tethered nucleophile. This approach allows the easy access to a wide range of heterocycles, including pyrrolidines, piperidines, tetrahydrofurans, morpholines, delta-valerolactones, and dioxanones. It is amenable to gram-scale preparation and complex fragment coupling.
Review
Chemistry, Inorganic & Nuclear
Gitanjali Jindal, Navneet Kaur
Summary: Compounds containing heteroatoms and their derivatives are important in organic chemistry, with N-heterocycles commonly used as recognition units for optical sensors and in biological applications. Pyrimidine derivatives are suitable for sensing materials and have various biological and medicinal applications, thanks to their ability to form coordination and hydrogen bonds. This review covers various pyrimidine-based optical sensors from 2005 to 2020.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Biochemistry & Molecular Biology
Carla Rizzo, Sara Amata, Ivana Pibiri, Andrea Pace, Silvestre Buscemi, Antonio Palumbo Piccionello
Summary: The incorporation of fluorine atoms or heterocyclic moieties into drug structures is a common pattern in medicinal chemistry. The combination of these two features is consistently observed in newly synthesized molecular entities with diverse biological activities, as evidenced by the increasing number of Fluorinated heterocyclic compounds approved by the FDA as drugs. This review highlights the biological activity and synthetic aspects of 33 recently FDA-approved fluorinated heterocyclic drugs from 2016 to 2022.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Organic
Marco Thomas Passia, Jan-Hendrik Schoebel, Niklas Julian Lentelink, Khai-Nghi Truong, Kari Rissanen, Carsten Bolm
Summary: In this study, TBS-protected or NH-sulfonimidamides were reacted with beta-alkoxyvinyl trifluoromethylketones under solvent-free mechanochemical conditions to produce 3-trifluoromethyl-substituted three-dimensional 1,2,6-thiadiazine 1-oxides. C4-functionalized products were obtained by starting from cyclic enones and brominations of the initially formed heterocycles. The stability of the products was investigated by varying the pH value and storage under aerobic conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Maxime Artault, Thomas Cantin, Melissa Longuet, Kassandra Vitse, Christ Daniel Matatu Mbengo, Frederic Guegan, Bastien Michelet, Agnes Martin-Mingot, Sebastien Thibaudeau
Summary: This study reports a method to reorganize the core structure of aliphatic unsaturated nitrogen-containing substrates by exploiting polyprotonation in superacid solutions. The superelectrophilic activation of N-isopropyl systems allows for the selective functionalization of nitrogen-containing substrates. It is demonstrated that this skeletal reorganization can be controlled through protonation interplay.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
