?
Symmetrical Tertiary Amines: Applications and Synthetic Approaches
European Journal of Organic Chemistry. 2021. Vol. 2021. No. 4. P. 543-586.
Tertiary amines represent a key class of organic molecules with multiple industrial, synthetic, and analytical applications. The focus of this review is on different approaches towards the synthesis of the C3 and C3V symmetrical tertiary amines. Generally, symmetrical tertiary amines can be prepared via N‐alkylation with alkyl halides and alcohols, reductive amination, desamination, hydroamination of olefins, and different kinds of C–N cross‐coupling reactions. All reactions leading to the titled structures are discussed, and the advantages and disadvantages of each method are provided.
Krasil’nikov V. N., Tyutyunnik A. P., Chulkov E. et al., Journal of Materials Science 2023
In this paper, the results of studying the formation conditions, crystal structure, thermal, spectral, and optical
properties, as well as the electronic band structure of cobalt-doped zinc glycolate Zn1-xCox(OCH2CH2O)
(0˂x≤0.2) are presented. It was established on the basis of X-ray powder diffraction data that the crystal
structure of Zn1-xCox(OCH2CH2O) is derived from the structure of Zn(OCH2CH2O), i.e. it ...
Added: March 29, 2023
Mikhaylov A. A., Dilman A., Khomutova Y. et al., European Journal of Organic Chemistry 2013 Vol. 2013 No. 25 P. 5670-5677
N‐Silylamines add to six‐membered nitronates with high diastereoselectivity. The reaction follows an original mechanism in which thermodynamic control plays the key role. ...
Added: September 30, 2020
Afanasyev O., Fatkulin Artemy R., Solyev P. et al., European Journal of Organic Chemistry 2020 Vol. 2020 No. 39 P. 6289-6294
The method of direct reductive amination of camphor and fenchone was proposed. The most effective reducing agent is iron carbonyl. No ligands or solvents are needed. The stereochemistry of the corresponding products was determined by HMBC, HSQC, and NOESY spectra. The limitations of the method were shown. The reaction of camphor with primary amines led ...
Added: January 11, 2022
Phosphine ligands in the ruthenium-catalyzed reductive amination without an external hydrogen source
Makarova M., Afanasyev O., Kliuev F. et al., Journal of Organometallic Chemistry 2021 Vol. 941 Article 121806
A systematic study of the phosphine additives influence on the activity of a ruthenium catalyst in reductive amination without an external hydrogen source was carried out. [CymeneRuCl2]2 was used as a reference catalyst, and a broad set of phosphines including Alk3P, Alk2ArP, Ar3P and X3P was screened. Three complexes of general formula (Cymene)RuCl2PR3 were isolated in a ...
Added: April 13, 2021
Fatkulin A., Afanasyev O., Tsygankov A. et al., Journal of Catalysis 2022 Vol. 405 P. 404-409
Catalytic reductive reactions are essential for laboratory and industrial-scale organic synthesis. However, the nowadays trend is the development of new, progressively more complicated reducing systems, which hinders the application of such highly efficient approaches in practice. Another way to achieve highly active systems is enhancing the activity of the earlier developed catalysts with simple structures. ...
Added: January 11, 2022
Shmal’ko A., Cendoya P., Anufriev S. et al., Chemical Communications 2022 Vol. 58 No. 23 P. 3775-3778
Two new approaches to the functionalization of the 1-carba-closodecaborate anion [1-CB9H10] at boron atoms via the ring-opening of its 1,4-dioxane derivative with various nucleophiles and Pd-catalysed cross-coupling of its iodo derivative with aromatic amines and heteroaromatics were developed. ...
Added: January 29, 2023
Stogniy M., Erokhina S., Suponitsky K. et al., Dalton Transactions 2021 Vol. 50 No. 14 P. 4967-4975
A number of new nido-carboranyl amidines 10-R(CH2)nNHC(Et)vHN-7,8-C2B9H11 (n = 2, R = OH, OMe, and NMe2; n = 3, R = OH) were synthesized by the nucleophilic addition of amino alcohols and N,N-dimethylethylenediamine to the highly activated –CuN+– triple bond of the 10-propionitrilium derivative of nido-carborane. A similar reaction of 10-EtCuN-7,8-C2B9H11 with ethylenediamine unexpectedly resulted in the cleavage of ...
Added: April 8, 2022
Afanasyev O., Kuchuk E., Usanov D. et al., Chemical Reviews 2019 Vol. 119 No. 23 P. 11857-11911
Reductive amination plays a paramount role in pharmaceutical and medicinal chemistry owing to its synthetic merits and the ubiquitous presence of amines among biologically active compounds. It is one of the key approaches to C–N bond construction due to its operational easiness and a wide toolbox of protocols. Recent studies show that at least a ...
Added: August 5, 2020
Vinogradov A., Komarov P., Puntus L. et al., MolBank 2022 Vol. 2022 No. 4 P. 1-7
A new terbium(III) complex with a (3,4-diphenyl)(2-methylthienyl)cyclopentadienyl ligand
was synthesized. Single-crystal X-ray analysis revealed a binuclear biscyclopentadienyl complex
with a [TbCl2K]2 core. Luminescence properties of the terbium complex were analyzed. ...
Added: January 28, 2024
Baraboshkin N., Zelenov V., Ivan V. Fedyanin, CrystEngComm 2023 Vol. 25 No. 48 P. 6719-6739
he main objective of this study is to investigate the potential of cinnoline oxides and their nitro derivatives as explosive materials. Thus, the study includes the synthesis, crystal structure prediction, single-crystal X-ray structure determination, crystal packing analysis and calculation of the detonation properties of [1,2,5]oxadiazolo[3,4-c]cinnoline 5-oxide, 1,5-dioxides and their nitro derivatives. It was found that ...
Added: January 18, 2024
Stogniy M., Anufriev S., Bogdanova E. et al., Dalton Transactions 2024 Vol. 53 No. 7 P. 3363-3376
A series of stable iron(II) bis(dicarbollide) derivatives [8,8’-(RNHC(Et)vHN)2-3,3’-Fe(1,2-C2B9H10)2] (R = Pr, R = Ph, (CH2)2OH, (CH2)3OH, (CH2)2NMe2) was prepared starting from FeCl2 or [FeCl2(dppe)] and the corresponding nido-carboranyl amidines [10-RNHC(Et)vHN-7,8-C2B9H11]. In a similar way, the reactions of the oxonium derivatives of nido-carborane with FeCl2 in tetrahydrofuran in the presence of t-BuOK lead to the corresponding stable oxonium derivatives iron(II) ...
Added: February 28, 2024
Evgeniya Podyacheva, Balalaeva A., Afanasyev O. et al., New Journal of Chemistry 2023 Vol. 47 P. 10514-10518
Current approaches to the reductive amination are often non selective, require complicated catalysts or not atom-economical. Application of syngas as a mild and selective reducing agent to aminate carbonyl compounds with unstable under hygrogenation conditions functional groups furnishing the broad substrate scope is demonstrated herein. Amino acid precursor and furfurylamine derivative were prepared indicating the ...
Added: October 25, 2023
Stogniy M., Anufriev S., Shmal’ko A. et al., Dalton Transactions 2021 Vol. 50 No. 7 P. 2671-2688
An unusual reactivity of 9-iodo-nido-carborane [9-I-7,8-C2B9H11]− towards nucleophiles under strong basic conditions was revealed. The nucleophilic substitution of iodine with O- and N-nucleophiles results in [9-RO-7,8-C2B9H11]− (R = H, CH2CH2OMe) and [9-L-7,8-C2B9H11] (L = Py, NEt3, Me2NCH2CH2NMe2), respectively. Reaction of [9-I-7,8-C2B9H11]− with CoCl2 in 1,2-dimethoxyethane in the presence of t-BuOK, depending on the order of addition of the reagents, ...
Added: April 17, 2022
Artemy R. Fatkulin, Korochantsev V., Afanasyev O. et al., New Journal of Chemistry 2023 Vol. 47 P. 6532-6535
Herein we report a transition-metal- and acid-free protocol for the reductive amination of carbonyl compounds with DMF using a substoichiometric amount of NaH2PO2-H2O. A set of various N,Ndimethylamines were obtained in moderate to excellent yields without chromatographic purification. The general trends and limitations of the method with different formamides as sources of dialkyl-fragments were explored. ...
Added: October 25, 2023
Kalinin M., Medved’ko A., Minyaev M. E. et al., Journal of Organic Chemistry 2023 Vol. 88 No. 11 P. 7272-7280
A new approach to the preparation of N,N′-unsymmetrically substituted 9-aminobispidines through aminal bridge removal reaction has been developed, the principal feature of which is the ability to selectively functionalize all three nitrogen atoms. The intermediates of 1,3-diazaadamantane’s aminal bridge removal reaction are characterized, and the mechanism of this reaction is proposed based on the analysis ...
Added: February 14, 2024
Faraonov M., Romanenko N., Mikhailenko M. et al., New Journal of Chemistry 2021 Vol. 45 P. 13599-13607
Reduction of organic dye trans-perinone (its abbreviation is perinone) in different experimental conditions allows us to obtain and characterize radical anion {cryptand(K+)}[perinone˙−] (1) and dianion {PPN+}2[perinone2−]·2C6H4Cl2 (2) salts of this dye. The salts have layered structures. Perinone˙− radical anions form π–π stacked dimers in 1 with an effective interaction between them, whereas perinone2− dianions are ...
Added: October 21, 2022
Astakhov A., Chernenko A., Kutyrev V. et al., Inorganic Chemistry Frontiers 2023 Vol. 10 No. 1 P. 218-239
C-Amino-1,2,4-triazoles are challenging polynitrogen substrates for metal-catalyzed arylation due to their multidentate character, enhanced coordinating ability and decreased nucleophilicity of the amino group. In the present study, the Buchwald–Hartwig cross-coupling of diverse 3(5)-amino-1,2,4-triazoles with aryl chlorides and bromides delivering (hetero)arylamino-1,2,4-triazoles in good-to-excellent yields under Pd/NHC catalysis was developed. The use of Pd complexes with bulky ...
Added: February 14, 2024
Nikolaev S. A., Tsodikov M. V., A. V. Chistyakov et al., Catalysis Today 2021 Vol. 379 P. 50-61
PdCu/Al2O3 (Pd = 0.1 wt.%, Cu = 0.1 wt.%) catalyst and its monometallic analogues (Pd/Al2O3 and Cu/Al2O3) were prepared by combination of deposition-precipitation and impregnation methods. The structure of the catalysts was studied by means of XRD, TEM, EDS, TPD-NH3, and DRIFTS. In a standard run (275 ○C, 5 h), Cu/Al2O3 converts 11 % of ethanol to α-alcohols with ...
Added: November 11, 2023
Svitanko I., Pivina T. S., Khakimov D. V., Journal of Molecular Modeling 2024 Vol. 30 Article 93
Using quantum chemistry and atom–atom potential methods, the molecular and crystal structures of cubane 1 and all types of unsubstituted azacubanes 2–22 were calculated. Alternative possible polymorphs of cubane 1 have been proposed. The thermochemical properties of azacubanes in the gas and solid phases were assessed. Thermodynamic aspects of stability are considered, and a significant ...
Added: March 13, 2024
Shirokova V., Ikonnikova V., Solyev P. et al., Synthesis 2021 Vol. 53 No. 24 P. 4689-4699
Directly accessible 8-substituted tetrahydroquinolines undergo 1,5-hydride shift-triggered cyclization to provide hardly accessible julolidine derivatives in 20-98% yield under scandium (III) triflate catalysis. The scope of the reaction, several follow-up transformations and a remarkable side-process discovered during the conditions optimization are highlighted. ...
Added: July 29, 2021
Андрюшечкин Б. В., Eltsov K., Pavlova T. et al., Journal of Chemical Physics 2018 Vol. 148 No. 24 Article 244702
The adsorption of O-2 on Ag(111) between 300 and 500 K has been studied with temperature-programmed desorption (TPD) and scanning tunneling microscopy (STM). At the first stage of adsorption, the disordered local oxide phase (commonly looking in STM as an array of black spots) is formed on the surface irrespective of the substrate temperature. The maximum concentration of black spots was found to be approximate to 0.11 ML, which corresponds to an oxygen coverage of approximate to 0.66 ML. Taking into account that the nucleation of the Ag(111)-p(4 x 4)-O phase starts after the saturation of the disordered phase, one ...
Added: October 25, 2021
I. V. Sedov, Arutyunov V. S., Tsvetkov M. V. et al., Eurasian Chemico-Technological Journal 2022 Vol. 24 No. 2 P. 157-163
The possibility of using coalbed methane to produce methanol is assessed. Methanol can be obtained from methane both by direct partial oxidation and from synthesis gas formed through the oxidative conversion of methane. Thermodynamic analysis of coalbed methane conversion was carried out to determine the conditions for obtaining synthesis gas with the ratio [H2 ]/[CO] = ...
Added: October 7, 2022
Tatiana L. Kulova, Skundin A., Gavrilin I. M. et al., Batteries 2022 Vol. 8 No. 8 Article 98
Nanostructure composites Ge-Co-P with brutto-composition CoGe2P0.1, or CoGe2@GeP were manufactured via electrolysis of aqueous electrolyte. Such composites are able to reversible insertion of lithium and sodium with specific capacities up to 855 and 425 mAh/g, respectively. The main advantage of the composites consists in their excellent cycleability. ...
Added: November 25, 2022
Budkov Y., Kolesnikov A. L., Polymer Science - Series C 2018 Vol. 60 No. Supplement 1 P. 148-159
Theoretical models of the conformational behavior of flexible polymer chains in mixed solvents enunciated in the world literature during the last decade are critically reviewed. Models describing different mechanisms of coil-to-globule transitions in a good solvent induced by cosolvent addition are highlighted. Special attention is given to the analysis of theoretical approaches to describing the ...
Added: November 30, 2018