Article
Chemistry, Multidisciplinary
Aibo Li, Xinjian Song, Qiao Ren, Peiwang Bao, Xinyu Long, Fuli Huang, Lvjiang Yuan, Jianrong Steve Zhou, Xurong Qin
Summary: A cobalt-catalyzed deuteration of amidoacrylates using deuterated methanol resulted in the synthesis of highly enantioselective α,β-dideuterio-α-amino esters with almost complete deuteration (99%). This new protocol was successfully employed for the preparation of dideuterio-α-amino acid fragments in certain drugs, and also applied in the concise synthesis of dideuterio L-DOPA.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Francesco Vaghi, Giorgio Facchetti, Isabella Rimoldi, Matteo Bottiglieri, Alessandro Contini, Maria Luisa Gelmi, Raffaella Bucci
Summary: Multiple studies have shown that the pyrrolidine nucleus is more efficient as organocatalysts for the condensation of aldehydes with electrophiles via enamine, compared to piperidine or morpholine. The low reactivity of morpholine-enamines is due to the presence of oxygen on the ring and the pyramidalisation of nitrogen, which decreases the nucleophilicity of the enamine. Therefore, finding efficient morpholine organocatalysts is a challenging task.
FRONTIERS IN CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Vladimir A. Larionov, Ben L. Feringa, Yuri N. Belokon
Summary: Asymmetric catalysis is a significant development in the field of chemistry, with chiral metal catalysts playing a crucial role. In metal-templated catalysts, the metal can act as a template, provide chirality, or enhance the acidity of the ligands.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Ane Garcia-Urricelqui, Abel de Cozar, Antonia Mielgo, Claudio Palomo
Summary: This study demonstrates that the chemistry of alpha-amino aldehydes can be expanded by conducting direct alpha-alkylation reactions with nitroolefins, leading to the generation of densely functionalized products with high diastereo- and enantioselectivity, containing up to two, quaternary and tertiary, vicinal stereocenters. The proposed mechanism suggests that intramolecular hydrogen bonding between the NH group and the carbonyl oxygen atom in the starting alpha-amino aldehyde is crucial for reaction stereocontrol.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Apoorva Malik, Pragati R. Sharma, Rakesh K. Sharma
Summary: We report a class of quaternary ammonium Cinchona-functionalized crown ether-strapped calix[4]-arene phase-transfer catalysts for the efficient enantioselective alpha-alkylation of glycine imines. The catalyst exhibits excellent catalytic performance at 0.1 mol % catalytic loading, affording the desired alpha-alkylated glycinates with 98% yield and 99.9% ee. The catalyst could be recovered and recycled up to 30 test cycles without a significant drop in activity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Anna S. Tovmasyan, Anna F. Mkrtchyan, Hamlet N. Khachatryan, Mary V. Hayrapetyan, Robert M. Hakobyan, Artavazd S. Poghosyan, Avetis H. Tsaturyan, Ela V. Minasyan, Victor I. Maleev, Vladimir A. Larionov, Armen G. Ayvazyan, Norio Shibata, Giovanni N. Roviello, Ashot S. Saghyan
Summary: A new family of Cu(II) and Ni(II) salen complexes was synthesized and characterized. These complexes were evaluated for their catalytic activity in the C-alpha-alkylation reaction of Schiff bases. It was found that introducing a chlorine atom into the phenyl ring of the substrate increased both the chemical yield and asymmetric induction. The highest enantiomeric excess was achieved using a Cu(II) salen complex based on (S,S)-cyclohexanediamine and salicylaldehyde at -20 degrees C. Bulky substituents in the ligand led to a decrease in both the enantioselectivity and chemical yield, with complete loss of stereoselectivity achieved with certain substituents at positions 3 and 5 of the phenyl ring.
Article
Chemistry, Applied
Irma Garcia-Monzon, Jorge Borges-Gonzalez, Tomas Martin
Summary: The heterogenization of homogeneous catalysts onto a solid support is a crucial step towards sustainable chemistry. In this study, we developed a series of polymer-supported tetrahydropyran-based hybrid dipeptides as active catalysts for the enantioselective Michael addition of aldehydes to beta-nitrostyrenes. The optimal anchor position and orientation between the catalyst and solid support, as well as the linker length, were carefully designed to enhance the catalytic efficiency. These supported catalysts exhibited high yields and enantiomeric excesses, and detailed deactivation studies provided important insights for prolonging their useful life.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ryan T. Davison, Patrick D. Parker, Xintong Hou, Crystal P. Chung, Sara A. Augustine, Vy M. Dong
Summary: In this study, the coupling of alpha-nitroesters and alkynes using Rh-H catalysis was employed to prepare alpha-amino-acid precursors. This atom-economical strategy allows for the generation of two contiguous stereocenters with high enantio- and diastereocontrol. The alkyne undergoes isomerization to form a Rh-III-pi-allyl electrophile which then reacts with an alpha-nitroester nucleophile, ultimately leading to the formation of allylic alpha-amino esters through reduction with In powder.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Gianluca Casotti, Vincenzo Rositano, Anna Iuliano
Summary: Stabilised arylzinc iodide prepared by direct insertion of zinc into aryl iodides, were successfully applied as nucleophiles in the Hayashi Rh-catalysed enantioselective conjugate addition to enones, with high yields and 99% ee of the addition product. The general applicability of the protocol was confirmed by using different arylzinc iodides and enones, as well as organometallic reagents with both halogen and electrophilic groups.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Tao Qin, Guowei Lv, Qi Meng, Ge Zhang, Tao Xiong, Qian Zhang
Summary: An efficient and general radical hydroamination of alkenes has been achieved using Co(salen) as catalyst, NFSI and its analogues as both nitrogen source and oxidant. Mechanistic experiments indicate that the reaction proceeds through a metal-hydride-mediated hydrogen atom transfer and a catalyst-controlled S(N)2-like pathway. Additionally, an unprecedented asymmetric version with good to excellent enantiocontrol was accomplished using a modified chiral cobalt(II)-salen catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Yiqi Ren, Maodi Wang, Qihua Yang, Junfa Zhu
Summary: The development of chiral solid catalysts using unconventional strategies is crucial for efficient heterogeneous asymmetric catalysis. The study presents a chiral solid catalyst, chiral diamine modified Ni/SiO2, for asymmetric Michael addition. The experimental results demonstrate that the peripheral Ni sites in close contact with SiO2 support are likely to be the active sites.
Article
Chemistry, Multidisciplinary
Zeng-Hua Wu, An-Qi Cheng, Meng Yuan, Ya-Xuan Zhao, Huai-Lan Yang, Li-Hua Wei, Huai-Yu Wang, Tao Wang, Zunting Zhang, Wei-Liang Duan
Summary: Utilizing the pyridinyl moiety as the coordinating group in cobalt-catalysed asymmetric nucleophilic addition/alkylation of secondary phosphine oxides can lead to the efficient synthesis of tertiary phosphine oxides with high yields and high enantiomeric excess, along with broad functional-group tolerance. Mechanistic studies reveal that (R)-secondary phosphine oxides preferentially interact with the cobalt catalysts to produce P-stereogenic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Desislav Dinev, Katya B. Popova, Tanya Zhivkova, Lora Dyakova, Abedullkader Abudalleh, Radostina Alexandrova, Daniela C. Culita, Teodora Mocanu, Catalin Maxim, Gabriela Marinescu
Summary: Two new families of Cu(II) and Co(II) mononuclear complexes with mixed ligands were successfully synthesized and characterized. Biological evaluation showed that these complexes exhibit cytotoxic effects on HeLa and LSR-SF-SR cells.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Sebastian Frankowski, Justyna Kowalska, Anna Albrecht
Summary: A novel method has been described for the preparation of enantiomerically enriched pyridine derivatives using 2-pyridylacetic acids as valuable synthons in an asymmetric fashion. The synthesis based on iminium activation using a chiral aminocatalyst successfully controlled the stereochemical outcome of the transformation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Ruslan A. Kovalevsky, Maxim Smirnov, Alexander S. Kucherenko, Kseniya A. Bykova, Elizaveta Shikina, Sergei G. Zlotin
Summary: In this study, 2-nitroallylic carbonates were used for the first time as promising biselectrophilic C3 synthons. They reacted with kojic acid derivatives in a bifunctional squaramide catalyzed asymmetric domino reaction, yielding nitro compounds that contain two hydroxypyranone units. The reaction products undergo noncatalytic epimerization at the carbon atom next to the nitro group. A plausible mechanism of the epimerization based on reversible formation of intermediate aci-nitro compound is proposed. The double addition products were transformed into configurationally stable acetates and chiral nitro glutarates, which are promising precursors for chiral amino glutaric acid derivatives.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Ekaterina V. Shevaldina, Vladimir A. Tsyganov, Natalia V. Kalganova, Alexander F. Smol'yakov, Natalia G. Frolova, Iliya A. Cherepanov
Summary: The first ferrocenes with mesoionic heterocyclic substituents were prepared by ferrocenyl alkylation of 4-mercapto derivatives of sydnones and sydnone imines. Several synthesized compounds exhibited strong antidote activity against metsulfuron-methyl (Zinger WP) herbicide.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Anna S. Tovmasyan, Anna F. Mkrtchyan, Hamlet N. Khachatryan, Mary V. Hayrapetyan, Robert M. Hakobyan, Artavazd S. Poghosyan, Avetis H. Tsaturyan, Ela V. Minasyan, Victor I. Maleev, Vladimir A. Larionov, Armen G. Ayvazyan, Norio Shibata, Giovanni N. Roviello, Ashot S. Saghyan
Summary: A new family of Cu(II) and Ni(II) salen complexes was synthesized and characterized. These complexes were evaluated for their catalytic activity in the C-alpha-alkylation reaction of Schiff bases. It was found that introducing a chlorine atom into the phenyl ring of the substrate increased both the chemical yield and asymmetric induction. The highest enantiomeric excess was achieved using a Cu(II) salen complex based on (S,S)-cyclohexanediamine and salicylaldehyde at -20 degrees C. Bulky substituents in the ligand led to a decrease in both the enantioselectivity and chemical yield, with complete loss of stereoselectivity achieved with certain substituents at positions 3 and 5 of the phenyl ring.
Article
Biochemistry & Molecular Biology
Gleb B. Yakovlev, Aleksei A. Titov, Alexander F. Smol'yakov, Andrey Yu. Chernyadyev, Oleg A. Filippov, Elena S. Shubina
Summary: The reaction between a cyclic trinuclear copper(I) or silver(I) pyrazolate complex and 1,1'-dimethyl-2,2'-bibenzimidazole can result in the formation of tetranuclear adducts decorated by one or two molecules of a diimine ligand. The coordination of the ligand can stabilize the formation of a tetrahedral core in the copper-containing complex and a distorted tetrahedron in the silver analog. Complexes with one diimine molecule possess two types of metals and exhibit significantly distorted central cores. Temperature decrease and solid-state structure activate triplet states, leading to phosphorescence. The silver-containing complex exhibits dual emission even at room temperature.
Article
Chemistry, Inorganic & Nuclear
Olga Khromova, Mikhail A. Emelyanov, Nadezhda Stoletova, Ekaterina E. Bodunova, Darya O. Prima, Alexander F. Smol'yakov, Igor L. Eremenko, Victor I. Maleev, Vladimir A. Larionov
Summary: A family of well-defined lambda- and delta-configured octahedral cationic chiral-at-cobalt catalysts were expanded through postcomplexation of bromine-functionalized Co(III) complexes. This is the first example of direct modification of the ligand sphere of chiral Co(III) catalysts through Suzuki-Miyaura cross-coupling reaction. The chiral metal center is observed to be epimerized during the cross-coupling process.
Article
Chemistry, Medicinal
Irina V. Sandulenko, Irina V. Belozertseva, Edwin E. Zvartau, Maria V. Zelentsova, Asmik A. Ambartsumyan, Alexander F. Smol'yakov, Sergey K. Moiseev
Summary: Thevinols and orvinols are important opioid receptor ligands, and the fluorinated compound 21,21,21-trifluoro-20-methylorvinol showed similar analgesic activity to morphine. However, its N(17)-allyl derivative had no analgesic activity.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Valentina A. Karnoukhova, Ivan V. Fedyanin, Ekaterina V. Dubasova, Aleksei A. Anisimov, Ivan V. Ananyev
Summary: Research suggests that the electronic virial-based correlation should be utilized for estimating bonding contributions to molecular vibrations in crystals.
MENDELEEV COMMUNICATIONS
(2023)
Article
Crystallography
Ivan V. Fedyanin, Aida I. Samigullina
Summary: Single crystals of two polymorphic forms of 4'-methyl-2,4-dinitrodiphenylamine were obtained and characterized. The two forms have different symmetry and contain the same supramolecular synthon. The crystal packing reveals quasi-isostructurality of the fragments joined by weak interactions.
Article
Chemistry, Inorganic & Nuclear
Arina Olbrykh, Aleksei Titov, Alexander Smol'yakov, Oleg Filippov, Elena S. Shubina
Summary: The investigation studied the interaction of cyclic trinuclear silver(I) pyrazolate [AgPz](3) with pyridine-based chalcones through various spectroscopic techniques. The carbonyl group participated in coordination with metal ions, while non-covalent pi-pi/M-pi interactions played a major role in complex formation. The structures of the complexes were retained in both solution and solid state. Isomerization affected the complexation of anthracene-containing chalcones, with E-isomer seeking a planar structure and Z-isomer showing chelating coordination. The complexation of anthracene-containing chalcones allowed a change in emission nature, while phenyl-substituted chalcone demonstrated a significant shift in emission energy compared to the free base when complexed with a macrocycle.
Article
Multidisciplinary Sciences
Hegine I. Hakobyan, Silva M. Jamgaryan, Armen S. Sargsyan, Yuri M. Danghyan, Vladimir A. Larionov, Victor I. Maleev, Ashot S. Saghyan, Zorayr Z. Mardiyan
Summary: Non-proteinogenic amino acids play a significant role in pharmaceutical synthesis and molecular catalyst development. This study presents an asymmetric metal-templated synthesis of a number of enantiomerically pure (S)-2-amino-2-methyl-5-arylpent-4-ynoic acids, which can increase the structural diversity in synthesizing pharmaceutically relevant peptides.
Article
Chemistry, Organic
Andrei V. Zaitsev, Sergey S. Kiselev, Alexander F. Smol'yakov, Yury V. Fedorov, Elena G. Kononova, Yurii A. Borisov, Valentina A. Ol'shevskaya
Summary: An efficient method for preparing 3,5-dicarborane-substituted BODIPY conjugates was developed by functionalizing 3,5-dibromo-8-pentafluorophenyl-BODIPY with carborane nucleophiles. The addition of a third carborane cluster to the BODIPYs was achieved by substituting the para-fluorine atom with the appropriate carborane nucleophile. The effects of carborane substitution on the absorption and fluorescence properties of the BODIPYs were analyzed, and the crystal structures of two BODIPY compounds were investigated.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Correction
Chemistry, Organic
Mikhail A. Arsenov, Nadezhda V. Stoletova, Tat'yana F. Savel'yeva, Alexander F. Smol'yakov, Victor I. Maleev, Dmitry A. Loginov, Vladimir A. Larionov
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Mikhail A. Arsenov, Nadezhda V. Stoletova, Alexander F. Smol'yakov, Tat'yana F. Savel'yeva, Victor I. Maleev, Dmitry A. Loginov, Vladimir A. Larionov
Summary: In this study, a protocol for the synthesis of non-proteinogenic alpha-amino acids with a 3,4-dihydroisoquinolone core was developed. The reaction was performed using a Rh(III)-catalyzed C-H activation/annulation reaction and resulted in high yields of diastereomeric complexes.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
