caa a22 4500 475760360 CHVBK 20180406123549.0 cr unu---uuuuu 170329e20000301xx s 000 0 eng 10.1007/BF02494768 doi (NATIONALLICENCE)springer-10.1007/BF02494768 Multiple bond migration with participation of a protophilic agent [Elektronische Daten] 5. Double bond migration in heteroallylic systems [V. Kobychev, N. Vitkovskaya, E. Larionova, B. Trofimov] The pathways of migration of the double bond in heteroallylic systems XCH2CH=CH2 (X =NMe2, OMe, PMe2, and SMe) with participation of hydroxide ion were investigated by theab initio RHF/6-31+G* and MP2/6-31+G* methods. The results are compared with those of analogous calculations of the systems with X=H, Me. Conformational isomerism of the initial molecules and reaction products, as well as the structure of intermediate carbanions, are considered. Increased acidity of compounds containing atoms of the third-row elements is explained in terms of a negative hyperconjugation model, 1,3-Hydrogen shift with participation of hydroxide ion in the system XCH2CH=CH2 results in double bond migration toward substituent X to form 1-hetero-1-propenes XCH=CHMe. Comparison of the energies of the final products indicates thermodynamic preferableness of the formation ofE-isomers. At the same time, in the case of substituents with atoms of the second-row elements the interaction of σ-bonds of the substituents and the p-AO of the terminal C atom additionally stabilizesZ-isomers of the carbanions and can be the reason for preferable kinetically controlled formation of these isomers. If the subsituents contain atoms of the third-row elements, the formation ofE-isomers of 1-hetero-1-propenes becomes both kinetically and thermodynamically predominant. Kluwer Academic/Plenum Publsihers, 2000 propene nationallicence but-1(2)-ene nationallicence 1-(dimethylamino)prop-1(2)-ene nationallicence 1-methoxypropo-1(2)-ene nationallicence 1-(dimethylphosphino)prop-1(2)-ene nationallicence 1-methylthioprop-1(2)-ene nationallicence 1,3-hydrogen shift nationallicence carbanion nationallicence acidity nationallicence hydroxide ion nationallicence reaction mechanism nationallicence ab initio quantum-chemical calculations nationallicence Kobychev V. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut Vitkovskaya N. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut Larionova E. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut Trofimov B. Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/3(2000-03-01), 415-420 1066-5285 49:3<415 2000 49 11172 https://doi.org/10.1007/BF02494768 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02494768 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Kobychev V. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Vitkovskaya N. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Larionova E. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Trofimov B. Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/3(2000-03-01), 415-420 1066-5285 49:3<415 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer