Review
Chemistry, Multidisciplinary
Wooseok Lee, Inyoung Park, Sungwoo Hong
Summary: Bifunctional reagents that can serve as dual coupling partners have become important tools in organic chemistry for efficient and sustainable synthesis. In particular, bifunctional reagents containing N-heteroaryl groups have attracted attention for their ability to introduce valuable N-heteroaryl moieties into complex molecules. These reagents have been successfully used in visible-light-mediated reactions to achieve difunctionalization of alkenes, alkynes, and [1.1.1]propellanes, providing access to highly functionalized N-heteroarenes. This review summarizes the recent advancements and applications of these bifunctional reagents in photoinduced difunctionalization, highlighting their potential as powerful synthetic tools.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Laura Santos, Florian Audet, Morgan Donnard, Armen Panossian, Jean-Pierre Vors, David Bernier, Sergii Pazenok, Frederic R. Leroux
Summary: An efficient method for the synthesis of high-value N-polyfluoroalkyl anilines, primary polyfluoroalkylamines, and N,N-bis(polyfluoroalkyl) amines via N-polyfluoroalkylation of sulfonamides and phthalimide derivatives using sulfuryl fluoride (SO2F2) is reported. The in situ formation of polyfluoroalkyl fluorosulfonates from commercially available fluorinated alcohols and economical sulfuryl fluoride is advantageous in terms of environmental impact and cost. This general method allows for the polyfluoroalkylation of a variety of substrates, providing valuable building blocks for life science applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xie Wang, Zongtao Lin, Katelyn A. Bustin, Nate R. McKnight, William H. Parsons, Megan L. Matthews
Summary: Electrophilic cofactors play important roles in physiological and disease processes. This study develops a platform for analyzing the reactivity and selectivity of nucleophilic probes towards main-chain carbonyl cofactors, which can help in the development of selective inhibitors.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yoshihiko Yamamoto, Syunji Tazawa, Ryu Tadano, Takeshi Yasui
Summary: Despite advances in trifluoromethylation methods, synthesizing complex trifluoromethylated molecules with a natural-product-like 3D structure is still challenging. This study investigated the cycloaddition of novel CF3-substituted oxidopyridinium betaines. By methylating trifluoromethylated pyridin-3-ols and reacting the generated pyridinium ions with triethylamine and N-methylmaleimide, trifluoromethylated 8-azabicyclo[3.2.1]octane derivatives were produced through a (5+2) cycloaddition. The regioselectivity and stereoselectivity of the reactions depended on the positions of the CF3 substituents, and computational investigations were conducted to gain further insight into the reactivity of trifluoromethylated oxidopyridinium betaines.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Ibrahim S. Al Nasr, Waleed S. S. Koko, Tariq A. A. Khan, Rainer Schobert, Bernhard Biersack
Summary: A series of fourteen pyrimido[1,2-a]benzimidazole compounds were synthesized using straightforward heterocyclic chemistry and oxidation methods. Among them, the new pyrimidobenzimidazole derivative 2a, with a 3-fluorophenyl substituent, exhibited excellent antiparasitic activity, showing high activity against Leishmania major parasites with EC50 values in the nanomolar concentration range. Compound 3b was less active against L. major but more active against Toxoplasma gondii, displaying considerable selectivity. Therefore, two promising and selective antiparasitic drug candidates, namely 2a and 3b, were identified for the treatment of two parasitic diseases, which can be prepared using green chemistry methods and simple one-pot reactions and oxidation procedures, respectively.
Article
Chemistry, Organic
Viera Polackova, Dominika Kristofikova, Boglarka Nemethova, Renata Gorova, Maria Meciarova, Radovan Sebesta
Summary: Bifunctional N-sulfinylureas and thioureas with an appended pyrrolidine unit were synthesized and evaluated as organocatalysts in Michael additions. The N-sulfinyl-urea catalyst was more efficient than the corresponding thiourea, achieving up to 98% ee enantioselectivities for some substrates. The mode of action was elucidated through DFT calculations, confirming a dual activation mode involving enamine activation of aldehydes and hydrogen-bond activation of nitroalkenes.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Organic
Buqing Cheng, Danhua Ge, Xin Wang, Xueqiang Chu
Summary: In recent years, a significant breakthrough has been made in synthesizing fluorine-containing heterocycles by utilizing perfluoroalkyl halides as key building blocks. This approach involves cleaving/functionalizing C-X bonds in perfluoroalkyl halides during perfluoroalkylation and cyclization processes to synthesize a range of fluorinated heterocycles.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Max Wienhold, Byeongseok Kweon, Calum McLaughlin, Matthias Schmitz, Till J. B. Zaehringer, Constantin G. Daniliuc, Christoph Kerzig, Ryan Gilmour
Summary: Amide groups are widely present in the chemical space continuum, and their structural and pharmacological importance as well as hydrolytic vulnerabilities drive the development of bioisosteres. Alkenyl fluorides have a long history as effective mimics, but emulating peptide bond isomerization with fluoro-alkene surrogates is challenging. This study presents a design of an ambiphilic linchpin that enables isomerization process, providing geometrically-programmable building blocks for small molecule amide and polyene isostere discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
De-Yin Chen, Shuai Song, Ling-Yan Chen, Xinfeng Ren, Ya Li
Summary: An efficient synthesis method for 2-arylacetonitriles containing a fluorinated stereogenic center has been developed through organo-catalyzed Michael addition reaction. The use of a cheap organocatalyst (DBU) allows for a broad substrate scope, including alpha, beta-unsaturated ketones, esters, nitriles, and sulfones. Importantly, water has been found to be a suitable solvent for this reaction.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Frederic Justaud, Rene Gree
Summary: The Meyer-Schuster Rearrangement (MSR) is a challenging process for propargylic alcohols with fluorine atom(s) on their chains. Phosphomolybdic acid was demonstrated to be an efficient catalyst for the MSR, providing fluorine-containing enones as useful intermediates for the synthesis of compounds with fluorine(s) on their side chains. This study has significant importance for the synthesis of target compounds with fluorine substituents.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Christopher Cremer, Monalisa Goswami, Christian K. Rank, Bas de Bruin, Frederic W. Patureau
Summary: This study reports the Te-II/Te-III-catalyzed dehydrogenative C-H phenothiazination of challenging phenols with electron-withdrawing substituents under mild aerobic conditions, achieving high yields. The unexpected Te-II/Te-III radical catalytic properties were characterized through cyclic voltammetry, EPR spectroscopy, kinetic experiments, and DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Sindija Lapcinska, Pavels Dimitrijevs, Linards Lapcinskis, Pavel Arsenyan
Summary: A straightforward and atom-economic method has been developed for the functionalization of short selenocystine-containing peptides, which shows good tolerance to unprotected peptides. This method is based on the generation of a selenium radical via visible light-initiated reaction in the presence of transition metal-free photocatalyst, and further oxidized to an electrophile that is trapped by N-heterocycles for functionalization. Mechanism confirmation includes NMR, HRMS, UV, EPR and cyclic voltammetry experiments as well as photocatalyst emission quenching studies.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Elias Abedelnour, Stephanie Ognier, Olivier Venier, Laurent Schio, Michael Tatoulian, Janine Cossy
Summary: This study presents the direct synthesis of trifluoromethyl N,N-aminals from nitrogen containing heterocycles using argon plasma in a continuous flow microreactor without any additives or metal catalysts. The transformation of these compounds to N-trifluoroethyl amines is also reported.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Si-Hui Tan, Zhao-Hui Chen, Huan Luo, Ting Liu, Guo-Qing Zhong
Summary: Two novel bismuth(III) complexes were synthesized and characterized. One of the complexes is an ionic compound, while the other is a coordination polymer. Through photocatalytic experiments, it was found that these complexes exhibit good activity in the degradation of certain organic dyes.
Review
Chemistry, Inorganic & Nuclear
Fatemeh Gholami, Shirin Ansari, Bagher Larijani, Mohammad Mahdavi
Summary: Sulfur-containing heterocycles are widely used in material science, biology, and pharmaceutics. Xanthate salts and xanthate esters, known for their stability and affordability, have been extensively studied for their applications in the synthesis of sulfur-containing heterocycles.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
