An unexpected rearrangement that disassembles alkyne moiety through formal nitrogen atom insertion between two acetylenic carbons and related cascade transformations

New approach to Sampangine derivatives and polycyclic aromatic amides

Sergei F. Vasilevsky, Denis S. Baranov, Victor I. Mamatyuk, Yury V. Gatilov, Igor V. Alabugin

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

(Chemical Equation Presented) This work analyzes multiple new reaction pathways which originate from intramolecular reactions of activated alkynes with the appropriately positioned multifunctional hemiaminal moiety. Combination of experimental substituent effects with Natural Bond Orbital (NBO) analysis revealed that alkyne polarization controls partitioning between these cascades. A particularly remarkable transformation leads to the formation of six new bonds at the two alkyne carbons due to complete disassembly of the alkyne moiety and formal insertion of a nitrogen atom between the two acetylenic carbons of the reactant. This reaction offers a new synthetic approach for the preparation of polycyclic aromatic amides with a number of possible applications in molecular electronics. Another of the newly discovered cascades opens access to substituted analogues of Sampangine alkaloids which are known for their antifungal and antimycobacterial activity against AIDS-related opportunistic infection pathogens.

Original languageEnglish
Pages (from-to)6143-6150
Number of pages8
JournalJournal of Organic Chemistry
Volume74
Issue number16
DOIs
Publication statusPublished - 1 Jan 2009
Externally publishedYes

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Alkynes
Amides
Nitrogen
Carbon
Derivatives
Atoms
Molecular electronics
Pathogens
Alkaloids
Polarization
sampangine

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "An unexpected rearrangement that disassembles alkyne moiety through formal nitrogen atom insertion between two acetylenic carbons and related cascade transformations: New approach to Sampangine derivatives and polycyclic aromatic amides",
abstract = "(Chemical Equation Presented) This work analyzes multiple new reaction pathways which originate from intramolecular reactions of activated alkynes with the appropriately positioned multifunctional hemiaminal moiety. Combination of experimental substituent effects with Natural Bond Orbital (NBO) analysis revealed that alkyne polarization controls partitioning between these cascades. A particularly remarkable transformation leads to the formation of six new bonds at the two alkyne carbons due to complete disassembly of the alkyne moiety and formal insertion of a nitrogen atom between the two acetylenic carbons of the reactant. This reaction offers a new synthetic approach for the preparation of polycyclic aromatic amides with a number of possible applications in molecular electronics. Another of the newly discovered cascades opens access to substituted analogues of Sampangine alkaloids which are known for their antifungal and antimycobacterial activity against AIDS-related opportunistic infection pathogens.",
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T1 - An unexpected rearrangement that disassembles alkyne moiety through formal nitrogen atom insertion between two acetylenic carbons and related cascade transformations

T2 - New approach to Sampangine derivatives and polycyclic aromatic amides

AU - Vasilevsky, Sergei F.

AU - Baranov, Denis S.

AU - Mamatyuk, Victor I.

AU - Gatilov, Yury V.

AU - Alabugin, Igor V.

PY - 2009/1/1

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N2 - (Chemical Equation Presented) This work analyzes multiple new reaction pathways which originate from intramolecular reactions of activated alkynes with the appropriately positioned multifunctional hemiaminal moiety. Combination of experimental substituent effects with Natural Bond Orbital (NBO) analysis revealed that alkyne polarization controls partitioning between these cascades. A particularly remarkable transformation leads to the formation of six new bonds at the two alkyne carbons due to complete disassembly of the alkyne moiety and formal insertion of a nitrogen atom between the two acetylenic carbons of the reactant. This reaction offers a new synthetic approach for the preparation of polycyclic aromatic amides with a number of possible applications in molecular electronics. Another of the newly discovered cascades opens access to substituted analogues of Sampangine alkaloids which are known for their antifungal and antimycobacterial activity against AIDS-related opportunistic infection pathogens.

AB - (Chemical Equation Presented) This work analyzes multiple new reaction pathways which originate from intramolecular reactions of activated alkynes with the appropriately positioned multifunctional hemiaminal moiety. Combination of experimental substituent effects with Natural Bond Orbital (NBO) analysis revealed that alkyne polarization controls partitioning between these cascades. A particularly remarkable transformation leads to the formation of six new bonds at the two alkyne carbons due to complete disassembly of the alkyne moiety and formal insertion of a nitrogen atom between the two acetylenic carbons of the reactant. This reaction offers a new synthetic approach for the preparation of polycyclic aromatic amides with a number of possible applications in molecular electronics. Another of the newly discovered cascades opens access to substituted analogues of Sampangine alkaloids which are known for their antifungal and antimycobacterial activity against AIDS-related opportunistic infection pathogens.

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