Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies

Andrés M. Álvarez-Constantino, Andrea Álvarez-Pérez, Jesús A. Varela, Giuseppe Sciortino*, Gregori Ujaque*, Carlos Saá*

*Corresponding author for this work

Research output: Contribution to journalArticleResearchpeer-review

4 Citations (Scopus)
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Abstract

The Ru-catalyzed intramolecular oxidative amidation (lactamization) of aromatic alkynylamines with 4-picoline N-oxide as an external oxidant has been developed. This chemoselective process is very efficient to achieve medium-sized ϵ- and ζ-lactams (seven- and eight-membered rings) but not for the formation of common δ-lactams (six-membered rings). DFT studies unveiled the capital role of the chain length between the amine and the alkyne functionalities: the longer the connector, the more favored the lactamization process vs hydroamination.

Original languageEnglish
Pages (from-to)1185-1193
Number of pages9
JournalJournal of Organic Chemistry
Volume88
Issue number2
DOIs
Publication statusPublished - 20 Jan 2023

Keywords

  • Acetylene
  • Amides
  • Amination
  • Cyclization
  • Hydroamidation
  • Indoles
  • Ketenes
  • Terminal alkynes
  • Transition-metal
  • Vinylidene rearrangements

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