Dissecting alkynes

Full cleavage of polarized C≡C moiety via sequential bis-michael addition/retro-mannich cascade

Saumya Roy, Maria P. Davydova, Runa Pal, Kerry Gilmore, Genrikh A. Tolstikov, Sergei F. Vasilevsky, Igor V. Alabugin

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

The reaction of diaryl ketoalkynes with 1,2-diamino ethane leads to the full scission of the triple bond with the formation of acetophenone and imidazoline fragments. In this transformation, one of the alkyne carbons undergoes formal reduction with the formation of three C-H bonds, whereas the other carbon undergoes formal oxidation via the formation of three C-N bonds (one π and two σ). Computational analysis confirmed that the key fragmentation step proceeds via a six-membered TS in a concerted manner. Both amines are involved in the fragmentation: the N-H moiety of one amine transfers a proton to the developing negative charge at the enolate oxygen, while the other amine provides direct stereoelectronic assistance to the C-C bond cleavage via a hyperconjugative nN → σ*C-C interaction.

Original languageEnglish
Pages (from-to)7482-7490
Number of pages9
JournalJournal of Organic Chemistry
Volume76
Issue number18
DOIs
Publication statusPublished - 16 Sep 2011
Externally publishedYes

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Alkynes
Amines
Carbon
Imidazolines
Ethane
Protons
Oxygen
Oxidation

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Dissecting alkynes : Full cleavage of polarized C≡C moiety via sequential bis-michael addition/retro-mannich cascade. / Roy, Saumya; Davydova, Maria P.; Pal, Runa; Gilmore, Kerry; Tolstikov, Genrikh A.; Vasilevsky, Sergei F.; Alabugin, Igor V.

In: Journal of Organic Chemistry, Vol. 76, No. 18, 16.09.2011, p. 7482-7490.

Research output: Contribution to journalArticle

Roy, Saumya ; Davydova, Maria P. ; Pal, Runa ; Gilmore, Kerry ; Tolstikov, Genrikh A. ; Vasilevsky, Sergei F. ; Alabugin, Igor V. / Dissecting alkynes : Full cleavage of polarized C≡C moiety via sequential bis-michael addition/retro-mannich cascade. In: Journal of Organic Chemistry. 2011 ; Vol. 76, No. 18. pp. 7482-7490.
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