Article
Chemistry, Organic
Wei Xie, Liang Zhao, Xinmei Fu, Rong Zhang, Xinyu Hao, Chunying Duan, Yaming Li
Summary: A new strategy for the synthesis of beta-amino alcohols and beta-amino ethers was developed, involving the three-component functionalization of olefins with sulfoxyimidoylsulfonium salt and a nucleophilic reagent using photoredox catalysis. The sulfoxyimidoylsulfonium salt plays a crucial role as the N-centred radical precursor. The strategy allows for the synthesis of beta-amino alcohols and beta-amino ethers with various functional groups in good yields under mild conditions, and offers the advantages of improved safety, no additives, and easy accessibility of raw materials.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Applied
Sk Abu Saleh, Atanu Hazra, Saumen Hajra
Summary: The catalyst and organic solvent-free regioselective hydroperoxylation method allows for the synthesis of secondary benzylic beta-hydroperoxy amines and alcohols, as well as tertiary 3-hydroperoxy oxindoles, and is also applicable to less reactive alkyl aziridines. Additionally, an acid-catalyzed Kornblum-DeLaMare type rearrangement of secondary benzylic hydroperoxide has been discovered to produce amino- and hydroxyl ketones.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Christopher J. J. Hall, William R. F. Goundry, Timothy J. Donohoe
Summary: Enantiopure 1,2-amino alcohols derived from abundant amino acids were used in C-C bond-forming hydrogen-borrowing alkylation reactions for the first time. The use of Ph*COMe aryl ketone facilitated the reactions, preventing racemisation of the amine stereocentre. The Ph* and trityl groups could be easily cleaved in one pot to give GABA products without further purification, allowing the two steps to be performed in sequence without isolation of the hydrogen-borrowing intermediate, eliminating the need for column chromatography.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xiai Luo, Zhongtao Yang, Jia Zheng, Gang Liang, Hui Luo, Weiguang Yang
Summary: CuX was used as a simple dual catalyst strategy for the tandem transformations of fused oxazolo[2,3-b][1,3]oxazines. Copper catalyzed the CuAAC/ring cleavage/[4+2] annulation reaction using terminal ynones, sulfonyl azides, and nitriles, while halogen catalyzed the ring cleavage and [2+3] annulation of oxiranes to form the final fused products. This study provides a four-component, one-pot strategy for synthesizing complex fused heterocycles from simple ingredients and expands the application of CuAAC in organic synthesis.
Article
Chemistry, Multidisciplinary
Yueyao Chen, Jesse Ling, Angus B. Keto, Yun He, Kam-Hung Low, Elizabeth H. Krenske, Pauline Chiu
Summary: Epoxy and aziridinyl enolsilanes can react as oxyallylic cation equivalents in highly selective and stereoselective intramolecular (3+2) cycloadditions. Computational studies suggest that the stepwise reaction involves the conformational flexibility of the intermediate, which determines the formation of (3+2) cycloadducts. This method can be used for the synthesis of densely functionalized trans-hydrindane scaffolds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Allwin D. McDonald, Samantha K. Bruffy, Aadhishre T. Kasat, Andrew R. Buller
Summary: In this study, we used a substrate multiplexed screening approach to improve the substrate scope overlap in biocatalytic cascades for the synthesis of chiral 1,2-amino alcohols. By engineering the activity of enzymes, we achieved selective and efficient synthesis of enantiopure products in a one-pot cascade reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Jing-Fei Wu, Nan-Wei Wan, Ying-Na Li, Qing-Ping Wang, Bao-Dong Cui, Wen-Yong Han, Yong-Zheng Chen
Summary: A dual-enzyme cascade strategy was developed for regiodivergent and stereoselective hydroxyazidation of alkenes, leading to the synthesis of various enantiomerically pure 1,2-azidoalcohols. This approach combines the asymmetric epoxidation of alkenes and regio-selective ring opening of epoxides with azide catalyzed by styrene monooxygenase and halohydrin dehalogenase. Additionally, a one-pot chemo-enzymatic route to chiral beta-hydroxytriazoles from alkenes was achieved by combining biocatalytic cascades and Cu-catalyzed azide-alkyne cycloaddition.
Article
Chemistry, Organic
Duc Chu, Jonathan A. A. Ellman
Summary: Unprotected, alpha,beta-disubstitutedtryptaminesand phenethylamines can be obtained through a one-pot, metal-free sequence involving in situ formation of aziridinium salts and subsequent Friedel-Crafts reaction with electron-rich (hetero)-arenes. The use of hexafluoroisopropanol as the solvent greatly facilitates both steps. This method is effective for variously substituted indoles and 1,3,5-trimethoxybenzene, as well as cyclic and acyclic alkenes, exhibiting stereospecificity for both (E)- and (Z)-1,2-disubstituted alkenes. Additionally, a diamine can be synthesized via one-pot morpholine addition to an aziridinium salt.
Article
Chemistry, Physical
Lia Martinez-Montero, Dirk Tischler, Philipp Suess, Anett Schallmey, Maurice C. R. Franssen, Frank Hollmann, Caroline E. Paul
Summary: A biocatalytic cascade was developed for the synthesis of enantioenriched azido alcohols, introducing chiral substituents through enzymatic epoxidation and regioselective cleavage reactions, leading to highly enantioenriched aromatic azido alcohols. This approach demonstrates the potential for practical production of these chiral compounds using two-component flavoprotein monooxygenases.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Organic
Arpita Banerjee, Gautam Panda
Summary: In this study, a base mediated, transition metal-free intermolecular epoxide ring opening reaction followed by intramolecular aromatic nucleophilic substitution (SNAr) was developed to synthesize separable diastereomers of selected benzo[b][1,4,5]oxathiazepine 1-oxides. This strategy allows the formation of both C-N and C-O bonds simultaneously in a single step. The method has a wide substrate scope, uses simple reaction conditions, and is applicable for synthesizing bioactive molecules with similar skeletons as benzoxathiazepine 1-oxides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Laura Ielo, Veronica Pillari, Margherita Miele, Davide Castiglione, Vittorio Pace
Summary: Homologation strategies provide versatile tools for introducing CH2 group into carbon skeletons in organic synthesis, resulting in diverse structural motifs through tuning of reaction conditions and homologating agent. By utilizing methods such as fluorinated carbenoids, three-membered cycles with fluorinated substituents can be efficiently assembled.
Article
Chemistry, Physical
Lyazid Ait Said, Mohamed Merouane El Hammoumi, Chaimaa El Haimer, Abdelhadi El Bachiri, Mostafa Khoukhi
Summary: Two new compounds of beta-amino alcohol were synthesized using (R)-(+)-alpha-methylbenzylamine as the starting material, and these compounds were found to react with a 1:1 mixture of cis and trans-limonene oxide in the presence of water, yielding beta-amino alcohols and unreacted limonene oxides or amines in the products.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Organic
Matthew J. Fleming, David M. Hodgson
Summary: The reaction involves the cross-coupling of alpha-lithiated terminal epoxides and N-(tert-butylsulfonyl)aziridines with alpha-lithio ethers to yield allylic alcohols and allylic amines. The mechanism proceeds through selective strain-relieving attack and beta-elimination of the lithium alkoxide.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yuxiang Zhu, Matthew J. S. Smith, Wenbin Tu, John F. Bower
Summary: TFA promotes deprotection of O-Ts activated N-Boc hydroxylamines, leading to aminofunctionalization-based polycyclizations of tethered alkenes. The method enables a range of intramolecular alkene anti-1,2-difunctionalizations, including diamination, amino-oxygenation, and amino-arylation. It offers a predictable platform for accessing diverse C(sp(3))-rich polyheterocycles relevant to medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Dongmin Kwak, Sehwa Jung, Hyeonbin Ha, Taedong Han, Do Hyun Ryu, Hyunwoo Kim, Jaesung Kwak
Summary: We present efficient synthetic methods for 1,2-aminoalcohols via electroreductive coupling between N-acyl diarylketimines and aldehydes. Mechanistic studies suggest that the reaction is initiated by selective electrochemical single electron transfer (SET) of N-acylketimines. The developed electrochemical protocol is compatible with biorelevant functional groups, allowing late-stage functionalization of pharmacophores.
Article
Chemistry, Organic
Maryna O. Mazur, Oleksii S. Zhelavskyi, Eugene M. Zviagin, Svitlana Shishkina, Vladimir Musatov, Maksim A. Kolosov, Elena H. Shvets, Anna Yu Andryushchenko, Valentyn A. Chebanov
Summary: A novel catalyst-free synthetic approach has been developed for the synthesis of 1,2,3-triazolobenzodiazepinones, using Ugi reaction and microwave-assisted intramolecular reaction. The study found that ruthenium-based catalysts were not necessary for the intramolecular reaction, making the isolation of target compounds more challenging. The microwave-assisted catalyst-free conditions were effective for both terminal and non-terminal alkynes.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Tibor Penaska, Vitalii Palchykov, Erik Rakovsky, Gabriela Addova, Radovan Sebesta
Summary: The stereoselective formation of spiro oxindole pyrrolidines via formal [3+2] cycloaddition of oxindole imines with ketoesters and ketoamides was investigated, with bifunctional squaramide organocatalyst inducing enantioselectivity of up to 72% ee. Ketoamides provided alternative products, and the reaction pathway was elucidated with the help of DFT calculation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yana I. Sakhno, Oleksandr V. Radchenko, Elena A. Muravyova, Svitlana M. Sirko, Svitlana V. Shishkina, Vladimir I. Musatov, Sergey M. Desenko, Valentyn A. Chebanov
Summary: In this study, [2-aryl-4-hydroxy-1-(5-methylisoxazol-3-yl)-5-oxo-2,5-dihydro-1H-pyrrol-3-yl]acetic acids and their esters were synthesized via a three-component reaction involving alpha-ketoglutaric acid or its diethyl ester, 3-amino-5-methylisoxazole, and aromatic aldehydes.
CHEMISTRY OF HETEROCYCLIC COMPOUNDS
(2021)
Article
Biochemistry & Molecular Biology
Dzung Nguyen, Xiulan Xie, Stephan Jakobi, Felix Terwesten, Alexander Metz, T. X. Phong Nguyen, Vitalii A. Palchykov, Andreas Heine, Klaus Reuter, Gerhard Klebe
Summary: Interfering with protein-protein interfaces for therapeutic intervention and drug design is attractive but challenging. In this study, a cysteine-containing protein variant was used to form a disulfide linkage under oxidizing conditions, leading to a novel packing geometry of the enzyme. By breaking up the homodimeric protein using the introduced disulfide cross-link, the study demonstrated the druggability of the interface and provided essential structural and design information through transformation into a quasi-monomeric state.
ACS CHEMICAL BIOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Eugene Zviagin, Vyacheslav Saraev, Dmytro Sysoiev, Blanka Klepetarova, Maryna Mazur, Oleksii Zhelavskyi, Yuliia Shliapkina, Thomas J. J. Mueller, Valentyn Chebanov
Summary: This research introduces a novel synthetic strategy for the preparation of polyazoles containing three or four nitrogen atoms in each azole cycle. Known procedures have been optimized to enhance conversion, selectivity, and overall efficiency.
Review
Chemistry, Multidisciplinary
Monica Rivas, Vitalii Palchykov, Xiangqing Jia, Vladimir Gevorgyan
Summary: This Review highlights recent advances in visible light-induced C(sp(3))-H bond activations, including amination of olefins and carbonyl compounds, and cross-coupling reactions. These methods rely on converting visible light into chemical energy to generate reactive but controllable radical species, providing a new synthetic platform for mild reaction conditions.
NATURE REVIEWS CHEMISTRY
(2022)
Article
Biochemical Research Methods
Daria Yu Miasnikova, Natalia A. Pinchukova, Vyacheslav E. Saraev, Vladimir Musatov, Hanna S. Vlasenko, Yuliia Shliapkina, Oleksandr Zbruyev, Valentyn A. Chebanov
Summary: A new analytical method was developed in this study to quantitatively determine the content of 1-methylcyclopropene (1-MCP) in a supramolecular complex using a multistep procedure involving gas release, chemical transformation, and HPLC analysis. The methodology allows reliable quantitative determination of 1-MCP in the complex with cucurbit[6]uril.
Article
Chemistry, Applied
Oleksandr Zbruyev, Konstantin Belikov, Serhii Khimchenko, Tamara Blank, Valentyn A. Chebanov
Summary: A modified procedure for the synthesis of cucurbit[6]uril on the kilogram scale was developed, which involved reducing the amount of chemicals used in the reaction and simplifying the subsequent workup steps. This procedure not only improved the yield of the product but also made the synthesis more environmentally friendly.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Organic
Yana Sakhno, Oleksandr Radchenko, Vyacheslav Saraev, Yuliia Shliapkina, Mariia Kaidash, Mariia Shyshkina, Svitlana Shishkina, Vladimir Musatov, Sergey Desenko, Valentyn Chebanov
Summary: This study describes the synthesis of novel peptidomimetics containing a pyrrolone fragment by a tandem combination of Doebner and Ugi type multicomponent reactions. The synthesis was performed at temperatures ranging from 25 to 45 degrees C and exhibited controlled diastereoselectivity. In most cases, each diastereomer could be isolated separately using this method.
Article
Chemistry, Multidisciplinary
Kateryna V. V. Dil, Yevhenii K. K. Kozyriev, Vitalii A. A. Palchykov
Summary: A simple method for synthesizing five- and six-membered ring sulfone carbamates was developed. The method involves the reaction of starting alcohols with trichloroacetyl isocyanate and subsequent hydrolysis of the protecting group using potassium carbonate in methanol. The cyclization of carbamates was catalyzed by Rh-2(OAc)(4). The study found that carbamates with saturated sulfone moiety tend to undergo elimination of carbamic acid, while unsaturated sulfone carbamates form a new heterocyclic system through aziridination pathway. In vitro pharmacological evaluation revealed that the new heterocyclic compound had good ADME properties, low acute toxicity, and a high probability of anticancer activity against prostate carcinoma cell line PC-3.
Review
Chemistry, Multidisciplinary
Serhiy M. Desenko, Mykola Yu. Gorobets, Victoria V. Lipson, Yana I. Sakhno, Valentyn A. Chebanov
Summary: Dihydroazolopyrimidines are an important class of heterocycles that are isosteric to natural purines and are therefore of great interest primarily as drug-like molecules. In the review, different ways to build dihydroazolopyrimidine systems from different building blocks are described, including aspects of green chemistry and non-classical activation methods. Information on the chemical properties of dihydroazolopyrimidines and the prospects for their use in the design of drugs of various profiles are also summarized in this review.
Article
Chemistry, Physical
Oleg A. Zhikol, Daria Yu. Miasnikova, Olga V. Vashchenko, Natalia A. Pinchukova, Oleksandr I. Zbruyev, Svitlana V. Shishkina, Alexander Kyrychenko, Valentyn A. Chebanov
Summary: Cucurbiturils are cage-like macrocyclic molecules that can form strong host-guest inclusion complexes. This study investigates the complexation between cucurbit[n]urils (CB[n], where n = 6-8) and biologically active substance PTTA. Molecular docking, quantum-chemical calculations, molecular dynamics simulations, and thermogravimetric analysis are employed to characterize the host-guest complexation. The study reveals the decreasing stability of the host-guest inclusion complex of PTTA with CB[n]s in the order CB[6]>CB[7]>CB[8].
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Crystallography
Mariia O. Shyshkina, Yana Sakhno, Oleksandr Radchenko, Svitlana Shishkina, Sergey M. Desenko, Valentyn A. Chebanov
Summary: The title compound, crystallized as a methanol solvate, may have biological activity inherent to natural peptides or proteins. In the crystal, molecules form hydrogen-bonded tetramers with solvate molecules acting as bridges. Hirshfeld surface analysis revealed different types of intermolecular interactions and their contributions.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2021)
Article
Crystallography
Mariia O. Shyshkina, Svitlana Shishkina, Konstantin S. Ostras, Nikolay Yu Gorobets, Valentyn A. Chebanov, Sergey M. Desenko
Summary: The coordination complex consists of a neutral tetrahydrotriazolopyrimidine derivative acting as a bridging ligand between two zinc molecules, resulting in polymeric chains. The zinc metal atom coordinates with the nitrogen atom of triazole and amino group, with the positive charge of the zinc atom being compensated by the chlorine anion and deprotonated acetic acid.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Vitalii Palchykov, Peter C. Dale, Jeremy Robertson
Summary: A stereodefined monodeuterated methyleneaziridine was prepared by coordinated reductive ring-opening of an alkynyl epoxide and diastereoselective tethered allene aziridination. Subsequent reaction of this aziridine with copper-based organometallics results in stereoretentive substitution, suggesting either an SNV pi mechanism or a C-N insertion/reductive coupling process.
NEW JOURNAL OF CHEMISTRY
(2021)
