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Vol 59, No 10 (2023)
Articles
Akademik RAN Boris Aleksandrovich Trofimov(k 85-letiyu so dnya rozhdeniya)
Žurnal organičeskoj himii. 2023;59(10):1249-1250
1249-1250
sec-Alkylketoximes in the Trofimov reaction: from minor products to reagents of the XXI century
Abstract
This review summarizes the results and perspectives of studies of the reaction between sec -alkylketoximes having only one C-H bond at the α-position to the oxime function and acetylene in the presence of superbasic catalytic media. Selective syntheses of key intermediates of pyrroles assembly (3 H -pyrroles and 5-hydroxypyrrolines), their reactivity, and unique cascade assemblies of unpredictable products are discussed.
Žurnal organičeskoj himii. 2023;59(10):1251-1268
1251-1268
Nucleophilic substitution of hydrogen in pyridine and its derivatives by organophosphorus nucleophiles in the presence of electron-deficient acetylenes
Abstract
The review considers publications on a new easy functionalization of pyridinoids (pyridines, quinolines, isoquinolines, acridine, phenanthridine) by the electron-deficient acetylene (esters of acetylenecarboxylic acids, acylacetylenes, cyanoacetylenes)/P-nucleophile (phosphine chalcogenides, H -phosphonates) system. Particular attention is paid to the SN H reaction of regioselective cross-coupling of pyridines with secondary phosphine chalcogenides, initiated by acylacetylenes and leading to the formation of 4-chalcogenophosphorylpyridines. In these processes, acetylenes act as trimodal adjuvants by (1) activating the pyridine ring towards P-nucleophiles, (2) deprotonating the P-H bond, and (3) facilitating the nucleophilic addition of the P-centered anion to the heterocyclic fragment, followed by the release of selectively reduced (to E -alkenes) acetylenes.
Žurnal organičeskoj himii. 2023;59(10):1269-1300
1269-1300
Quantum chemical investigations of the mechanisms of carboand heterocycles assemblies based on acetylenes reactions in superbasic media
Abstract
The chemistry of acetylenes has received significant development in the context of the use of superbasic media in organic synthesis. The study of reaction mechanisms requires the use of a complex of chemical, physicochemical, and theoretical methods. This review presents the results of recent quantum-chemical studies on mechanisms of assemblies based on the reactions of acetylene and its derivatives occurring in superbasic media and yielding in the formation of complex deeply functionalized molecular structures, which are being developed at the Irkutsk Institute of Chemistry named after A.E. Favorsky SB RAS.
Žurnal organičeskoj himii. 2023;59(10):1301-1318
1301-1318
Acetylenic and allenic carbanions in the reaction with heterocumulenes: a simple way to fundamental heterocycles
Abstract
The synthetic potential of adducts of acetylenic and allenic carbanions with isothiocyanates and azatrienic systems based on them - precursors of fundamental aza- and thiaheterocycles - pyrroles, 2,3-dihydropyridines, pyridines, quinolines, 3 H -azepines, 4,5-dihydro-3 H -azepines, 2-azabicyclo[3.2.0]hept-2-енов, thietanes, thiophenes, thiophene-2(5 H )-imines, 1,3-thiazoles, 4,5-dihydro-1,3-thiazoles, and other heterocyclic structures with rare and/or difficult-to-build functional and pharmacophore substituents is briefly described.
Žurnal organičeskoj himii. 2023;59(10):1319-1350
1319-1350
Double Mirozoki-Heck arylation of terminal alkenes using “ligand-free” pd catalytic systems
Abstract
The results of one-pot consecutive double arylation of terminal alkenes with aryl halides leading to three-substituted alkenes are presented. The advantages of the method when comparing with existing analogues are the combination of low reactive but available aryl bromides and aryl chlorides and «ligand-free» catalytic systems based on Pd(II) salt.
Žurnal organičeskoj himii. 2023;59(10):1351-1356
1351-1356
New macrocyclic bis-1,10-phenanthroline-2,9-diamides. synthesis and stereodynamics in solutions
Abstract
New examples of macrocyclic 1,10-phenanthroline-2,9-diamides containing simultaneously two phenanthroline moiety in their structure have been obtained. The structure of the obtained compounds was confirmed by NMR spectroscopy and other methods. New macrocyclic phenanthrolines expectedly exhibit complex stereodynamic behavior in solutions. This effect was studied using 1H NMR spectroscopy at various temperatures.
Žurnal organičeskoj himii. 2023;59(10):1357-1362
1357-1362
Theoretical study of electronic structure and ionization spectrum of γ-pyrone
Abstract
The electronic structure and ionization spectrum of γ-pyrone (4 H -pyran-4-one) were studied using the third-order algebraic-diagrammatic construction method for a one-particle Green’s function [IP-ADC(3)] and a number of other high-level quantum chemical methods. The results of the calculations are used to interpret the recently obtained photoelectron spectra. A number of new assignments are proposed concerning the nature of the photoelectron maxima of γ-pyrone above 12 eV, where, according to our calculations, there is a significant violation of the single-electron ionization picture due to electron correlation effects. The results obtained significantly change the interpretation of the spectrum available in the literature.
Žurnal organičeskoj himii. 2023;59(10):1363-1374
1363-1374
One-pot synthesis of (E)-3-(N-vinylpyrro-2-yl)acrylic acids
Abstract
The paper describes the synthesis of a previously unknown class of N -vinylpyrrolyl acrylic acids - multifunctional monomers and promising building blocks for fine organic synthesis, which was created on the basis of the fundamental works of academician Trofimov B.A., namely the synthesis of an inexhaustible class of N -vinylpyrroles.
Žurnal organičeskoj himii. 2023;59(10):1375-1380
1375-1380