Article
Chemistry, Multidisciplinary
Jianhong Su, Yuncong Luo, Xin Xu
Summary: An efficient and selective benzylic C(sp(3))-H addition of o-CH3-substituted tertiary aromatic amines to alkenes has been achieved using a scandium catalyst supported by an anilido-oxazoline ligand, providing an atom-economic method for the synthesis of a new family of alkylated tertiary anilines. A wide range of amine and alkene substrates are compatible with the catalyst system.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Chen-Fei Liu, Xiaohua Luo, Hongyu Wang, Ming Joo Koh
Summary: This study presents a catalytic protocol using a dimeric Ni(I) complex and an exogenous alkoxide base for the selective hydroarylation of unactivated and activated olefins. The reaction leads to the formation of products containing aryl- and alkenyl-substituted tertiary and quaternary centers, with high yields and regioisomeric ratios. The mechanism involves carbonickelation followed by hydride transfer using alkoxide as the hydride source, showcasing the utility of this single-catalyst protocol for the synthesis of medicinally relevant scaffolds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiaobo Pang, Zhen-Zhen Zhao, Xiao-Xue Wei, Liangliang Qi, Guang-Li Xu, Jicheng Duan, Xue-Yuan Liu, Xing-Zhong Shu
Summary: A reductive approach for branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R-X electrophiles is reported in this study, showing a new selectivity pattern for diene functionalization. The combination of Ni(0) and the phosphine-nitrile ligand resulted in >20:1 regioselectivity, allowing for the conjugation of two biologically active units to form more complex polyene molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Tatyana S. Koptseva, Natalia L. Bazyakina, Mikhail V. Moskalev, Evgeny V. Baranov, Igor L. Fedushkin
Summary: The paragraph describes the formation of two complexes from the reaction of [LGa-GaL] (1) with different ligands, characterized by H-1 NMR, IR spectroscopy, and single-crystal X-ray analysis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
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, Organic
Xiao-Di Nie, Zhuo-Ya Mao, Jia-Ming Guo, Chang-Mei Si, Bang-Guo Wei, Guo-Qiang Lin
Summary: A regioselective C-H alkenylation of N,N-dialkylanilines with ynamides using AgNTf2 as a catalyst has been developed. This approach allows for the introduction of an alkenyl group exclusively at the para position of aniline derivatives, resulting in the synthesis of a series of 4-alkenyl N,N-dialkylanilines with excellent regioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Bingnan Du, Chun-Ming Chan, Yuxin Ouyang, Kalok Chan, Zhenyang Lin, Wing-Yiu Yu
Summary: This study presents a novel method for the synthesis of high-value amides through NiH-catalyzed anti-Markovnikov intermolecular hydroamidation of unactivated alkenes. The protocol allows for the direct synthesis of structurally diverse N-alkyl amides using abundant carboxylic acid feedstocks and has shown success with both unactivated alkenes and natural products. Mechanistic studies suggest that the observed regioselectivities are controlled by the sterical environment of the coupling reaction.
COMMUNICATIONS CHEMISTRY
(2022)
Review
Chemistry, Physical
Josef Bernauer, Jennifer Polker, Axel Jacobi von Wangelin
Summary: Recent studies have shown that alpha-diimine ligands (BIANs) exhibit great versatility and applicability in metal complexes, primarily due to their ability to undergo electronic manipulations and their significant contributions to the synthesis of small and functionalized organic molecules through metal-BIAN catalysts.
Article
Chemistry, Organic
Hong-Chao Liu, Xiao-Ping Gong, Yu-Zhao Wang, Zhi-Jie Niu, Heng Yue, Xue-Yuan Liu, Yong-Min Liang
Summary: A novel Ru-catalyzed regioselective alkylarylation of vinylarenes with alkyl halides and arenes via meta-C(sp(2))-H bond functionalization has been reported. This reaction shows excellent substrate tolerance and regioselectivity, as well as redox-neutral conditions.
Review
Chemistry, Physical
Annaluisa Mariconda, Marco Sirignano, Rubina Troiano, Simona Russo, Pasquale Longo
Summary: This review summarizes the research progress from 2007 to 2022 on the nucleophilic addition of amines and water to terminal and internal alkynes catalyzed by N-heterocyclic carbene gold (I/III) complexes. These reactions are environmentally sustainable and lead to important intermediates in the chemical and pharmaceutical industry.
Article
Chemistry, Inorganic & Nuclear
Andrew T. Henry, Dana A. R. Nanan, Kim M. Baines
Summary: Various applications of bis(catecholato)germanes in catalysis were investigated, including hydrosilylation of benzaldehydes, hydroboration of phenylacetylene derivatives, and Friedel-Crafts alkylation using arylalkenes and either diphenylamine or anisole. Additionally, the catalytic activity of bis(catecholato)germanes with weak donor ligands in the oligomerization of α-methylstyrene was further studied, leading to the observation of trimer species formation in DCM. VTNA and Hammett analyses were performed, and an updated mechanism for bis(catecholato)germane catalysis was proposed.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Cesar Ruiz-Zambrana, Macarena Poyatos, Eduardo Peris
Summary: A gold complex with a naphthalene-di-imide-functionalized N-heterocyclic carbene (NHC) ligand was prepared and its reversible redox properties and catalytic activity in the hydroamination of terminal alkynes were studied.
Article
Chemistry, Organic
Kun Hu, Ruiting Liu, Xigeng Zhou
Summary: The rare earth metal-catalyzed reaction allows for the straightforward synthesis of new functional dibenzo[c,e]azepines from 2-nitrile-2'-alkenyl-(alkynyl) biphenyls and amines, avoiding the need for additives and demonstrating high yield and selectivity.
Article
Chemistry, Organic
Yetkin Gok, Beyhan Yigit, Ozlem Ozeroglu Celikal, Murat Yigit
Summary: A series of new rhodium(I) complexes with benzimidazole based N-heterocyclic carbene (NHC) ligand were synthesized and tested as catalysts in the intermolecular hydroamination reactions between styrene with aromatic amines in ionic liquid, showing catalytic activity and selective anti-Markovnikov addition products.
Article
Chemistry, Multidisciplinary
Li-Wen Zhan, Chuan-Jun Lu, Jia Feng, Ren-Rong Liu
Summary: This study reports for the first time that palladium compounds can catalyze the hydroarylation of 1-alkynylindoles with organoborons, resulting in the synthesis of chiral C-N atropisomers. The reaction conditions are mild and lead to excellent regio-, stereo- (Z-selectivity), and enantioselectivity. The simplicity, high stereoselectivity, and good functional group tolerance of this catalytic system make it highly attractive.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Anton N. Lukoyanov, Yulia Zvereva, Diana A. Parshina, Anton Cherkasov, Sergey Yu Ketkov
Summary: The reduction of dpp-MIAN with metallic calcium yields tetrameric complex 1, and further addition of dpp-MIAN leads to the formation of paramagnetic species 2. Both complexes show catalytic activity towards phenylacetylene and acetylene, and demonstrate catalytic activity in the polymerization of L-lactide.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ivan V. Lapshin, Anton V. Cherkasov, Konstantin A. Lyssenko, Georgy K. Fukin, Alexander A. Trifonov
Summary: A series of NHC-stabilized amido compounds showed remarkable catalytic efficiency in the addition of PhPH and PH3 to alkenes. The sigma-donor capacity of NHCs was found to have an effect on catalytic activity. The complex (NHG)(2)Sm[N(SiMe3)(2)] (5Sm) was identified as the most efficient catalyst.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
A. Maleeva, O. Yu Trofimova, I. Ershova, K. Arsenyeva, K. Pashanova, I. A. Yakushev, A. Cherkasov, R. R. Aysin, A. Piskunov
Summary: A series of new paramagnetic six-coordinate gallium complexes based on 3,6-di-tert-butyl-o-benzoquinone with N-donor ligands were synthesized and characterized. The structures of the compounds were determined by single-crystal X-ray diffraction. The synthesized compounds exhibit spin density delocalization between differently charged redox-active ligands.
RUSSIAN CHEMICAL BULLETIN
(2022)
Article
Chemistry, Inorganic & Nuclear
Jerome Long, Alexander N. Selikhov, Anton Cherkasov, Yulia Nelyubina, Fabrice Salles, Yannick Guari, Joulia Larionova, Alexander A. Trifonov
Summary: The synthesis and structures of two base-free alkoxide dysprosium(III) complexes are reported, and the magnetic properties of one of the complexes are investigated, revealing the occurrence of a field-induced slow relaxation of the magnetization.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
N. A. Protasenko, S. Baryshnikova, A. Cherkasov, A. Poddel'skii
Summary: The reaction of functionalized o-iminophenols with triphenyltin(IV) bromide in the presence of a base leads to the formation of triphenyltin complexes. The crystal structures of complexes II and III were determined by X-ray diffraction.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
K. Arsenyeva, A. Klimashevskaya, M. A. Zherebtsov, M. G. Chegerev, A. Cherkasov, I. A. Yakushev, A. Piskunov
Summary: The newly synthesized low-valent germanium complex exhibits versatile reactivity towards acid-base and redox transformations. The reactions with various reagents result in different products, showing diverse reaction characteristics under different experimental conditions. The molecular structures of the compounds are determined by X-ray diffraction.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ivan V. Lapshin, Anton V. Cherkasov, Alexander A. Trifonov
Summary: Treatment of 4,5-dimethyl-1,3-bis(2-pyridylmethyl)-1H-imidazolium chloride with M[N(SiMe3)2]2(THF)2 (M = Ca, Yb) in 1:2 molar ratio results in the formation of a carbene fragment, activation of the picolyl CH bond, and dearomatization of one of the pyridine rings and affords bis(amido) complexes [(NHC)MN(SiMe3)2]2 (M = Ca (2), Yb (3)) coordinated by a mu 2-bridging pincer NHC amido ligand. Complexes 2 and 3 demonstrate high catalytic activity and excellent regio- and chemoselectivities in the intermolecular hydrophosphination of styrene with both primary and secondary phosphines. Complexes 2 and 3 enable selective addition of PhPH2, Ph2PH, (CH2)4NH, and (CH2)5NH to para-divinylbenzene with high conversions under mild conditions. Tandem hydrophosphination/hydroamination of para-divinylbenzene was also performed.
Article
Chemistry, Inorganic & Nuclear
Dmitry M. Lyubov, Dmitry O. Khristolyubov, Anton V. Cherkasov, Alexander A. Trifonov
Summary: A series of Sc(III) and Y(III) heteroalkyl complexes were synthesized and their structures were determined by single crystal X-ray analysis. The reactivity of different Ln-C (diphenylmethanide vs alkyl or benzyl) bonds towards PhSiH3 was investigated. It was found that the sigma-bond metathesis reactions of certain complexes with PhSiH3 selectively involved Ln-C-Alkyl/Benzyl bonds, while the Ln-C-Ar2 bonds remained intact.
Article
Chemistry, Multidisciplinary
A. G. Morozov, D. A. Razborov, D. Ya. Aleynik, M. N. Egorikhina, D. D. Linkova, I. L. Fedushkin
Summary: A mechanism of ring-opening polymerization of lactide in a solution using a magnesium coordination compound (dpp-bian)Mg(thf)(3) (1) containing a chelating redox-active acenaphthenediimine ligand dpp-bian (1,2-bis-[(2,6- diisopropyl)phenylimino]acenaphthene) has been proposed. The reaction proceeds in the presence of a chain initiator/regulator ROH (R = H, alkyl, acyl), while the true polymerization catalyst is presumably the product of the interaction of complex 1, lactide, and ROH. It has been demonstrated that a decrease in the content of the initiating impurity in the initial monomer by precise purification of the latter makes it possible to control the molecular weight of polymer in order to obtain high molecular weight polylactide (M-w = 1.9 center dot 10(5), PDI 1.5). The resulting polymer shows no cytotoxicity, as confirmed by in vitro studies, due to its non-toxic catalyst system.
RUSSIAN CHEMICAL BULLETIN
(2023)
Article
Chemistry, Inorganic & Nuclear
O. Yu. Trofimova, A. V. Maleeva, K. V. Arsen'eva, A. V. Klimashevskaya, A. V. Cherkasov, A. V. Piskunov
Summary: New heteroleptic metal-organic frameworks of lanthanides with anionic organic ligands of two types are synthesized by solvothermal synthesis in N,N-dimethylformamide (DMF). The structures of three compounds, including a cross-linked coordination polymer and two scaffold derivatives, are studied by X-ray diffraction (XRD).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Galina A. Gurina, Alexey V. Markin, Anton V. Cherkasov, Ivan A. Godovikov, Anatoly M. Ob'edkov, Alexander A. Trifonov
Summary: Bis(phenolate) ligands containing benzimidazole-2-ylidene and tetrahydropyrimidine-2-ylidene linkers were used to synthesize isolable Sc3+ chloro and alkyl complexes. The chloro complexes (LScCl)-Sc-1,2(solv)(2) were obtained from the reaction of Sc(CH2SiMe3)(3)(THF)(2) with [(LH3)-H-1,2]Cl or by the salt metathesis reactions of ScCl3 with [L-1,L-2]Na-2. The alkyl derivative [(LSc)-Sc-2(CH2SiMe3)](2) was prepared through the alkylation reaction of (LScCl)-Sc-2(THF)(2) with LiCH2SiMe3 or by subsequent reactions of [(LH3)-H-2]Cl with NaN(SiMe3)(2) and Sc(CH2SiMe3)(3)(THF)(2).
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: By using X-ray crystallography, the cocrystals 1 center dot C6F6, 2 center dot C6F6, and 1 center dot(OFA)(2) were obtained by crystallizing the half-lantern Pt-2(II) complexes with electron-deficient arenes. The structural data revealed the occurrence of π-π stacking between the arenes and metal square-planes. Density functional theory calculations and orbital interaction analysis confirmed the contribution of noncovalent bonding and charge-transfer interaction in the overall stacking forces.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: In this study, it was observed by X-ray crystallography that the Pt-2(II) complexes form crystals with electron-deficient arenes, and it was verified that there is a π-π stacking interaction between the arenes and the metal square-planes. Density functional theory calculations confirmed the contribution of the noncovalent bond between the arenes and Pt(II) in the overall stacking forces. Orbital interaction analysis demonstrated the significance of the charge-transfer interaction between d(z)(2)(Pt) and pi*(C), attributing the C.Pt contact to a metal-involved tetrel bonding. Many-body interaction analysis showed a positive cooperative effect between the fragments of the half-lantern complex and the perfluoroarenes favoring the occurrence of supramolecular chains.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
I. V. Ershova, A. V. Maleeva, R. R. Aysin, A. V. Cherkasov, A. V. Piskunov
Summary: The synthesis and detailed characterization of a five-coordinated gallium(III) complex (AP(Me))GaI(bipy) have been presented in this study. The complex contains two redox-active ligands, 4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-iminobenzoquinone dianion (AP(Me)) and 2,2'-bipyridyl, along with an iodine atom in the coordination sphere. The molecular structure of the compound was determined through single-crystal X-ray diffraction analysis. Compound 1 exhibits stability in the crystalline state, but decomposes in solution due to symmetrization. The difference in color observed between the crystalline and solution states is attributed to possible intermolecular charge transfer in the crystalline state.
RUSSIAN CHEMICAL BULLETIN
(2023)
Article
Chemistry, Multidisciplinary
Jerome Long, Dmitry M. Lyubov, Alexander A. Kissel', Ilia A. Gogolev, Andrey A. Tyutyunov, Yulia Nelyubina, Fabrice Salles, Yannick Guari, Anton Cherkasov, Joulia Larionova, Alexander A. Trifonov
Summary: This study reports the synthesis, crystal structures, magnetic properties, and theoretical investigations of five erbium complexes. The coordination geometry of the complexes can be controlled by adjusting experimental conditions, with each complex exhibiting different magnetic behaviors and coordination structures.
