Article
Chemistry, Multidisciplinary
Shao-Qian Yang, Ai-Jun Han, Yang Liu, Xin-Yuan Tang, Guo-Qiang Lin, Zhi-Tao He
Summary: In this study, a comprehensive investigation was conducted towards the stereoselective formal hydration and hydroaminoxylation of conjugated dienes by synthesizing new P,N-ligands and identifying an aryl-derived oxime as a surrogate for water and hydroxylamine. Additionally, the asymmetric hydroalkoxylation with new P,N-ligands was elucidated. Furthermore, versatile derivatizations following hydration provided indirect but concise routes to formal hydrophenoxylation, hydrofluoroalkoxylation, and hydrocarboxylation of conjugated dienes that have not been reported before. Finally, a ligand-to-ligand hydrogen transfer process was proposed based on preliminary mechanistic experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Wei Sun, Meng-Yang Hu, Zhan-Sheng Lu, Ming-Yao Huang, Xin-Yu Zhang, Shou-Fei Zhu
Summary: This article reports a method for stereoselective transformation using an iron catalyst to synthesize Z-allylsilanes with high regioselectivity and exclusive stereoselectivity from E/Z mixtures. The mechanism of this reaction differs from previously reported mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Gautam Kumar, Zheng-Wang Qu, Stefan Grimme, Indranil Chatterjee
Summary: Catalytic hydroarylation reactions of conjugated dienes using tris(pentafluorophenyl)borane as a Lewis acid catalyst show a broad substrate scope for highly regioselective functionalization of sterically hindered aniline derivatives. Experimental and theoretical studies reveal the crucial role of residual water and B(C6F5)(3) complex in the reaction mechanism.
Article
Chemistry, Organic
Mei-Hua Shen, Xiao-Wen Qi, De-Xia Li, Xin-Yi Wang, Chi-Fan Zhu, Hua-Dong Xu
Summary: A new cobalt-catalyzed hydroazidation of 1-aryl-1,3-dienes using TMSN3 as a nucleophilic azide source has been reported, resulting in the synthesis of a variety of allylic azides with moderate to good yields. This oxidative MHAT hydroazidation demonstrates excellent regioselectivity towards 1,2-addition products through an S(N)2-like pathway between in situ generated allyl cobalt(iv) species and TMSN3.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Qiuyu Li, Xinxin Fang, Rui Pan, Hequan Yao, Aijun Lin
Summary: This study reports a Pd-catalyzed sequential hydroamination reaction that can efficiently synthesize various imidazolidinones, thiadiazolidines, and imidazolidines. Asymmetric sequential hydroamination generates a series of enantioenriched imidazolidinones with synthetic value.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Rodney A. Fernandes, Naveen Chandra, Ashvin J. Gangani, Gulenur N. Khatun
Summary: An efficient method for the synthesis of (E)-(3-alkoxybut-1-enyl)benzenes has been developed via Pd-catalyzed regioselective intermolecular hydroalkoxylation of 1-arylbutadienes. This method offers a simple operation, without the need for dry reaction conditions, and shows good tolerance to various substrates. The presence of chloromethyl methyl ether (MOMCl) as an additive is crucial to the success of the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yun-Xing Ji, Jinxia Li, Chun-Min Li, Shuanglin Qu, Bo Zhang
Summary: This study presents a visible-light-promoted method for generating amidyl radicals from N-fluorosulfonamides via a manganese-catalyzed N-F bond activation strategy, using a simple manganese complex and a cheap silane as reactants. This method enables the intramolecular/intermolecular hydroaminations of alkenes, two-component carboamination of alkenes, and even three-component carboamination of alkenes, allowing for the preparation of a wide range of valuable aliphatic sulfonamides.
Article
Materials Science, Characterization & Testing
Guangqian Zhu, Liang Wang, Qaiser Mahmood, Li Zhou, Qinggang Wang
Summary: Confined iminopyridine iron complexes with skeleton of 8-(arylimino)-5,6,7-trihydroquinolyl were synthesized and characterized, serving as highly efficient pre-catalysts for conjugated dienes polymerization. Adjusting substituents of ligand framework allowed for control of stereoselectivity, achieving high activity and molecular weight in polymerization reactions. The Fe1/MAO catalytic system showed excellent thermostability and high activity in polymerizing bio-based monomers, delivering green rubber with high molecular weights.
Article
Multidisciplinary Sciences
Yufeng Sun, Jun Guo, Xuzhong Shen, Zhan Lu
Summary: In this study, a method for sequentially catalyzing alkynes with nitrogen and silicon atoms using a cobalt catalyst is presented. The method involves two catalytic cycles with different ligands, and demonstrates high efficiency, simple operation, and excellent functional group tolerance. The study also reveals a phenomenon of ligand relay, where certain ligands can capture metal ions from other ligands.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiao Yan, Xiu-Ming Yang, Peng Yan, Bo Zhao, Rong Zeng, Bin Pan, Ying-Chun Chen, Lei Zhu, Qin Ouyang
Summary: In this study, it is demonstrated that 1,3-dienes form p-Lewis base-activated electron-neutral and HOMO-raised ?(2)-complexes with Pd(0), which undergo protonation with various acidic sources. The resulting p-allyl palladium complexes then undergo the amination reaction to give the final products. The mechanistic proposal is supported by FMO and NPA analyses, control experiments, and the development of an efficient Pd(0)-mediated hydroamination reaction.
Article
Chemistry, Organic
Ke-Qin Wu, Hui Li, Ao Zhou, Wei-Ran Yang, Qin Yin
Summary: A Pd-catalyzed regioselective C-H bond allylic alkylation of phenols with 1,3-dienes is reported, which selectively functionalizes the ortho C-H bond of 2-naphthols, 1-naphthols, and electron-rich phenols to synthesize phenol derivatives with diverse structures. The reaction is accelerated by a diphosphine ligand, does not require any other additive, and exhibits broad substrate scope and good chemo- and regioselectivity. Additionally, an asymmetric variant is investigated, achieving product with up to 55% enantiomeric excess.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
En-Kai Xiao, Xian-Tao Wu, Feng Ma, Xiaohua Feng, Peng Chen, Yi-Jun Jiang
Summary: The hydroamination of alkenes with carbazoles catalyzed by Fe(OTf)(3) and gamma-cyclodextrin is efficient, delivering a high yield of N-alkylated carbazoles and N-alkylated-carbazole-fused aromatics. This sustainable and green method features simple and benign reaction conditions without the need for a strong base, additive, or light irradiation.
Review
Chemistry, Multidisciplinary
Ian A. Tonks
Summary: This study discusses the recent progress in Ti-catalyzed oxidative amination reactions, highlighting the importance of understanding the reactive species and mechanisms involved. The research shows that low-valent Ti intermediates can be stabilized through coordination and that reductive elimination processes occur through pi-type electrocyclic reactions. These findings are crucial for advancing catalytic applications involving titanium.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Physical
Diego G. Matesanz, Laura Gamarra, Teresa Martinez del Campo, Pedro Almendros, Sara Cembellin
Summary: A highly selective Mn(I)-catalyzed dienylation of arenes and heteroarenes with acetylated allenes is reported. The method proceeds through a one-pot procedure and delivers linear 1,3-dienes as single products with high stereoselectivity and total regioselectivity. This strategy shows wide functional group tolerance and preparative scale utility, making it efficient for late-stage functionalization of complex valuable molecules. The synthetic importance is highlighted by different derivatizations of the final products, which can exhibit interesting fluorescence properties.
Article
Chemistry, Organic
Chuan-Jin Hou, Alexander W. Schuppe, James Levi Knippel, Anton Z. Ni, Stephen L. Buchwald
Summary: A method for stereoselective hydroalkenylation of alkynes using enol triflates was reported in this study. The formation of Z,Z- or Z,E-1,3-dienes with excellent stereoselectivity and yield was achieved by leveraging an in situ-generated and geometrically pure vinyl-Cu(I) species. This approach allowed for the synthesis of highly substituted Z-dienes, including pentasubstituted 1,3-dienes, which are challenging to prepare using existing methods.
Article
Chemistry, Medicinal
Anna Yu. Spivak, Darya A. Nedopekina, Rinat R. Gubaidullin, Eldar V. Davletshin, Adis A. Tukhbatullin, Vladimir A. D'yakonov, Milyausha M. Yunusbaeva, Lilya U. Dzhemileva, Usein M. Dzhemilev
Summary: This study synthesized F16-conjugated pentacyclic triterpenoids for the first time, showing significant antitumor activity against leukemia and cancer cells with high selectivity.
MEDICINAL CHEMISTRY RESEARCH
(2021)
Article
Chemistry, Medicinal
Vladimir A. D'yakonov, Regina A. Tuktarova, Lilya U. Dzhemileva, Svetlana R. Ishmukhametova, Usein M. Dzhemilev
Summary: In this study, hybrid molecules containing 5Z,9Z-dienoic acids were synthesized for the first time, showing high in vitro inhibitory activity against human topoisomerase I. These molecules were found to be efficient apoptosis inducers in various cell cultures and may have potential as novel drugs for human oncological diseases. Additionally, the synthesized acids were also investigated for their effects on mitochondria and potential DNA damage in tumor cells.
Article
Biochemistry & Molecular Biology
Gulnara N. Kadikova, Vladimir A. D'yakonov, Usein M. Dzhemilev
Summary: The catalytic [6 pi + 2 pi]-cycloaddition of N-carbocholesteroxyazepine with functionally substituted terminal alkynes and 1,4-butynediol was achieved for the first time using the Co(acac)(2)(dppe)/Zn/ZnI2 three-component catalytic system. The reaction yielded previously undescribed but promising 9-azabicyclo[4.2.1]nona-2,4,7-trienes covalently bound to natural metabolite cholesterol, with the structure confirmed by NMR spectra analysis.
Article
Oncology
Vladimir A. D'yakonov, Alexey A. Makarov, Lilya U. Dzhemileva, Ilfir R. Ramazanov, Elina Kh. Makarova, Usein M. Dzhemilev
Summary: The world is currently focusing on effective treatment regimens for oncological diseases, with multidrug resistance posing a significant challenge. Synthesizing new low molecular weight compounds that can target cellular pathways and activate signaling pathways is a potential solution for addressing drug resistance in tumor cells. New Z-stereoselective synthesis methods were developed for unsaturated acids containing a 1Z,5Z,9Z-triene moiety, showing promising inhibitory activities against human topoisomerase I and mitochondria.
Article
Engineering, Chemical
Rishat Aminov, Ravil Khusnutdinov
Summary: A new method has been developed for the complete hydrogenation of unsaturated hexacyclic norbornadiene dimers using sulfuric acid as the hydrogen donor, resulting in high yields of pentacyclo[8.2.1.1(5,8).0(2,9).0(3,7)]tetradecanes. Under specific conditions, the hydrocarbons can be transformed into benzene and aromatic products of unknown structure. Additionally, pentacyclo[8.2.1.1(5,8).0(2,9).0(3,7)]tetradecanes can be selectively isomerized to diamantane in high yield using [Et3NH](+)[Al2Cl7](-)-CuCl2 ionic liquid.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2021)
Article
Chemistry, Inorganic & Nuclear
Tat'yana P. Zosim, Ilfir R. Ramazanov, Rita N. Kadikova, Firuza T. Sadykova, Lidiya Z. Musina, Usein M. Dzhemilev
Summary: A novel method for cyclopropanation of unactivated 1-bromoalkenes using Me3Al and CH2I2 was developed, leading to the synthesis of substituted cyclopropyl bromides and 2-cyclopropylethyl iodides in good yield. The proposed mechanism involves the 2-cyclopropylethyl rearrangement of the cyclopropane-containing organoaluminum compound.
INORGANICA CHIMICA ACTA
(2021)
Article
Chemistry, Inorganic & Nuclear
Liliya I. Khusainova, Leila O. Khafizova, Tatyana Tyumkina, Rustam R. Salakhutdinov, Usein M. Dzhemilev
Summary: The Cp2TiCl2-catalyzed cycloboration of alpha,omega-dienes with boron halides BX3 (X = F and Cl) or RBCl2 (R = Et and n-Pent) in the presence of metallic Mg leads to the formation of 1,2-disubstituted boriranes. The alpha,omega-dichloroborane reacts with alpha-olefins under the same reaction conditions to produce mono-boriranes connected by a hydrocarbon chain with an oxaborinane ring.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Artur A. Khuzin, Airat R. Tuktarov, Olga V. Venidiktova, Valery A. Barachevsky, Ilnur N. Mullagaliev, Timur R. Salikhov, Renat B. Salikhov, Leonard M. Khalilov, Liliya L. Khuzina, Usein M. Dzhemilev
Summary: Hybrid molecules based on fullerene C-60 and dithienylethene and its perfluorinated analog were synthesized and used to fabricate organic field-effect transistors (OFETs). The OFETs based on the perfluorinated analog showed higher efficiency compared to those based on dithienylethenes.
PHOTOCHEMISTRY AND PHOTOBIOLOGY
(2022)
Review
Chemistry, Multidisciplinary
U. M. Dzhemilev, L. I. Khusainova, K. S. Ryazanov, L. O. Khafizova
Summary: The studies published over the past 15 years have summarized the synthesis, physicochemical properties, and application prospects of boron-containing carbocycles with one boron atom, including boriranes, borirenes, boretanes, and 1,2-dihydroboretanes. Various original synthesis methods were discussed, such as photochemical isomerization, double hydroboration, cycloaddition reactions, and Cp2TiCl2-catalyzed cycloboration. Additionally, data on the synthesis of four-membered boracyclanes were presented based on thermal isomerization, cycloaddition reactions, and transmetallation.
RUSSIAN CHEMICAL BULLETIN
(2021)
Editorial Material
Chemistry, Multidisciplinary
Rishat I. Aminov, Ravil I. Khusnutdinov
Summary: Diamantane, a three-spiro compound, was synthesized through skeletal isomerization of a new precursor pentacyclo[6.6.0.0(2,6).0(3,13).0(10,14)]tetradecane composed entirely of five-membered rings. The isomerization was induced by ionic liquids based on salts of aluminum, iron, nickel, manganese, zinc, tin, and copper, with aluminate ionic liquids being the most efficient, yielding up to 85% of diamantane.
MENDELEEV COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Nataliya N. Makhmudiyarova, Irina R. Ishmukhametova, Lilya U. Dzhemileva, Vladimir A. D'yakonov, Alexander O. Terent'ev, Usein M. Dzhemilev
Summary: An efficient method has been developed to synthesize N-aryl-1,2,4-dioxazolidines, N-aryl-tetraoxaspiroalkanes, and N-aryl-hexaoxadispiroalkanes with high cytotoxic activity against tumor cells by cycloaminomethylation of OH acids with 1,3,5-triaryl-1,3,5-triazinanes in the presence of lanthanide catalysts.
Article
Biochemistry & Molecular Biology
Vnira R. Akhmetova, El'mira M. Galimova, Ekaterina S. Mescheryakova, Lilya U. Dzhemileva, Usein M. Dzhemilev, Vladimir A. D'yakonov
Summary: In this study, the 1-(dimethylamino)methyl-6-quinolinol scaffold of topotecan, an anticancer drug, was modified to form copper-containing compounds for investigation of their cytotoxic properties. Mononuclear and binuclear Cu(II) complexes with 1-(N,N-dimethylamino)methyl-6-quinolinol and Cu(II) complexes with 1-(dimethylamino)methyl-2-naphtol ligand were synthesized and their structures confirmed. The compounds were tested for in vitro cytotoxic activity against various cancer cells, and the induction of apoptosis and effect on cell cycle were investigated. Mononuclear Cu(II) complex with 1-(N,N-dimethylamino)methyl-6-quinolinol ligand showed higher sensitivity, and all synthesized Cu(II) complexes exhibited higher antitumor activity compared to topotecan, camptothecin, and cisplatin.
Article
Chemistry, Organic
I. I. Islamov, A. V. Yusupova, V. A. D'yakonov, U. M. Dzhemilev
Summary: Previously unknown hybrid compounds based on monocarbonyl curcumin analog and long-chain (5Z,9Z)-alka-5,9-dienoic acids were synthesized for the first time in yields of 61-67%. The required unsaturated acids were prepared through a series of reactions, with the key step being the Cp2TiCl2-catalyzed intermolecular cross-cyclomagnesiation of aliphatic 1,2-dienes and 2-(hepta-5,6-dien-1-yloxy)tetrahydro-2H-pyran.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
L. I. Tulyabaeva, R. R. Salakhutdinov, T. V. Tyumkina, A. R. Tulyabaev, U. M. Dzhemilev
Summary: The cycloboration of methylidenecycloalkanes with PhBCl2 in the presence of Cp2TiCl2 as catalyst is reported for the first time, yielding previously unknown spiro-boracarbocycles in 70-80% yields. The structures and properties of the obtained spiro-boriranes were studied using B-11, H-1, and C-13 NMR and DOSY experiments. It was found that 1-phenyl-substituted boraspiranes were stable in solution at room temperature for 24 hours.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Rita N. Kadikova, Ilfir R. Ramazanov, Azat M. Gabdullin, Oleg S. Mozgovoj, Usein M. Dzhemilev
Summary: This study compares the catalytic effects of NbCl5 and Cp2ZrCl2 on the reaction pathway of N,N-disubstituted 2-alkynylamines with Et2Zn, revealing the differences in the formation of (2Z)-alkenylamines and their dideuterated and diiodinated derivatives.
