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New Reactions in Chemistry of Acetylenes

Explore new reactions in the chemistry of acetylenes, including dyad polynucleophile activation and unexpected bond cleavage pathways. Investigate highly sensitive systems with donor/acceptor substituents. Collaboration studies reveal unique substrate reactions and steric effects.

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New Reactions in Chemistry of Acetylenes

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  1. New Reactions in Chemistry of Acetylenes Sergey F. Vasilevsky, Maria P. Davydova Institute of Chemical Kinetics & Combustion, Novosibirsk, SB RAS

  2. Всесоюзная Конференция по химии ацетилена. Душанбе, 1968г.

  3. 45 лет спустя

  4. Dyad Polynucleophile - Activated Acetylene with AdjacentAcceptor Groups - Highly Sensitive System, Posessing an Increased Response to Internal and External Factors – Convenient Model for Investigation of Multichanel Reactions Acetylenes with donor and acceptor substituents Reagents – polyfunctional compounds with different nature of nucleophiles and/or distance between them.

  5. Reaction of α-Ketoacetyleneswith EDA Leads only to linear bis-adducts, according to literature data Basyouni M.N., Fouli F.A. Acta Chim. Acad. Sci. Hung., 1980, 105, 235

  6. Discovery of Unexpected Easy Full Cleavageof Triple Bondin α-KetoacetyleneunderInfluence of EDAi Michael addition Bis-adduct S. Roy, M.P. Davydova, R. Pal, K. Gilmore, G.A. Tolstikov,S.F. Vasilevsky, I.V. Alabugin. J. Org. Chem., 2011, 76 7482 S.F. Vasilevsky, M.P. Davydova, D.N.Tomilin, L.N. Sobenina, V.I. Mamatuyk,ARKIVOC, 2014, 5, 132

  7. Study of Reaction with Substrates BearingAroyl Moieties without Methoxy Groups (collaboration with L.N. Sobenina (IrICh SB RAS) S.F. Vasilevsky, M.P. Davydova, D.N. Tomilin, L.N. Sobenina, V.I. Mamatuyk,N.V. Pleshkova. ARKIVOC, 2014, 5, 1324

  8. Sensitivity of Reaction to Steric Effects of Substituents At first time was found product of attack amino group at C=O S.F. Vasilevsky, M.P. Davydova, D.N. Tomilin, L.N. Sobenina, V.I. Mamatuyk,ARKIVOC, 2014, 5, 132

  9. Proposed Pathway of the Complete Disproportionation of Alkyne Moiety (Collaboration with I.Alabugin, USA) Formal reduction of C-atom of С≡С with formation of three C-H bonds whereas the other one undergoes formal oxidation via the formation of three C-N bonds (one π and two σ) 5-exo-trig-cyclization S. Roy, M.P. Davydova, R. Pal, K. Gilmore, G.A. Tolstikov,S.F. Vasilevsky, I.V. Alabugin. J. Org. Chem., 2011, 76 7482

  10. Other Substrates – Another Products S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Aust. J. Chem. 2017, 70 421 Possible Pathway of the Formation of 2-phenyl-7H-dibenzo[de,h]quinolin-7-one

  11. Possible Pathway of the Complete Disproportionation of Alkyne Moiety S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Aust. J. Chem. 2017, 70 (4), 421-429

  12. Other Nucleophile – Another Composition of ProductsInteraction of α-Ketoacetylenewith 1,3-diaminopropaneRoute to tetrahydropyrimidines Формирование тетрагидропиримидинового цикла Davydova M.P., Vasilevsky S.F. unpublished data

  13. Study of the Directions Reactions of Substituted2-Aminoethanoles with α-Ketoacetylenes (collaboration with V.G.Nenaidenko) Collaboration with Prof. I.V.Alabugin

  14. Regioselective Addition of 2-Aminoethanole and N-Methyl-2-Aminoethanole to α-Ketoacetylenes without Cleavage(Collaboration with Prof. I.V.Alabugin, USA) S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Mend. Comm., 2015, 25 (5), 377

  15. New Reaction ofα-Ketoacetylenes Accompanied by a Complete Cleavage of Triple Bond. High Sensitivity to Steric Effect of Aminoethanol S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Mend. Comm., 2015, 25 (5), 377

  16. Possible Pathway of the Cleavage of Alkyne Moiety S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Mend. Comm., 2015, 25 , 377

  17. Trifluoromethyl Derivatives of α-Ketoacetylenesin Reaction with Substituted 2-Aminoethanoles(collaboration with Prof. V.G. Nenaidenko, MGU)

  18. M.P. Davydova, S.F. Vasilevsky, V.G. Nenajdenko. Journal of Fluorine Chemistry, 2016, 190, 61–67

  19. Possible Pathway of Fragmentation M.P. Davydova, S.F. Vasilevsky, V.G. Nenajdenko. Journal of Fluorine Chemistry, 2016, 190, 61–67

  20. Systematic study of reaction of EDAwith acetylenes bearing removed functional groups different structure Collaboration with Prof. I.V.Alabugin 2017

  21. Possible route of selective cleavage of TB in EDA with 2-Alkynyl-9,10-anthraquinones, in which the keto group is removed from the triple bond

  22. The conjugated nitro group activates the cleavage of the triple bond even in the presence of donor groups in both rings S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Aust. J. Chem. 2017, 70 (4), 421-429

  23. Fragmentation of 4-phenylethynyl pyridineThe full conversion depends on the reaction time S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Aust. J. Chem. 2017, 70 (4), 421-429

  24. The transformation of 2-phenylethynylpyridine leads to the Michael adduct and the product of its hydrolysis S.F. Vasilevsky, M.P. Davydova, I.V. Alabugin, et al. Aust. J. Chem. 2017, 70), 421-429 Conformity of the concept Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy of Functional Groups. S Z. Vatsadze, I.V.Alabugin. et al Chem. Eur. J. 2016, 22, 1 – 22

  25. Специфика реакции алкинов с аминоэтилентиолом – отсутствие расщепления тройной связи Не опубликованные данные 25

  26. Специфика диацетиленовых производных Необычная гетероциклизация, связанная не с расщеплением С≡С связи, а - С-С связи в нуклеофиле Не опубликованные данные 26

  27. New repertoire in classical piece of reaction of acetylenic compounds with EDA and PDA • Открыты новые р-ции расщепления ТС электроно дефицитных ацетиленов, под действием ЭДА и ПДА. Трансформации носят общий характер. • Фрагментация сопровождается образованием Ме группы из углерода ТС, ближайшего к акцепторной группе, а другой - участвует в формировании имдазолинового остова для ЭДА и пиримидиового – для ПДА.

  28. Similarities, and Differences in Cleavage of TB In Reaction with Ethanolamines Открыты новые реакции расщепления ТС под действием этаноламинов Фрагментация ароилацетиленов с этаноламинамми сопровождается образованием Ме группы из углерода ТС соседнего с С=О группой, а другой С - формированием амидного остатка (с участием молекулы воды). Напротив, фрагментация трифторацетилалкинов сопровождается образованием амидного фрагмента из углерода ТС соседнего с С=О группой, а другой - участвует в формировании СН3С=О группы (с участием молекулы воды). Во всех случаях для фрагментации важную роль играет С=О группа, атом кислорода которой погашает развивающийся отриц заряд в ПС. При разрыве ТС также важную роль играет стероэлектронное содействие свободной пары эл-оа атома азота.

  29. Thank you for attention This work was supported by grantRFBR №13-03-00129 (2013-2015 and grantRFBR №16-03-00589(2016-2018). 29

  30. Proposed Route of Formation by O-5-exo-dig-attack of 1-Phenyl-7H-dibenzo[de,h]isoquinolin-3,7-dione

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