Ruthenium-catalyzed oxidative coupling of primary amines with internal alkynes through C-H bond activation: Scope and mechanistic studies

Sara Ruiz, Pedro Villuendas, Manuel A. Ortuño, Agustí Lledõs, Esteban P. Urriolabeitia

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

The oxidative coupling of primary amines with internal alkynes catalyzed by Ru complexes is presented as a general atom-economy methodology with a broad scope of applications in the synthesis of N-heterocycles. Reactions proceed through regioselective C-H bond activation in 15 minutes under microwave irradiation or in 24 hours with conventional heating. The synthesis of 2,3,5-substituted pyridines, benzo[h]isoquinolines, benzo[g]isoquinolines, 8,9-dihydro-benzo[de]quinoline, 5,6,7,8-tetrahydroisoquinolines, pyrido[3,4g]isoquinolines, and pyrido[4,3g]isoquinolines is achievable depending on the starting primary amine used. DFT calculations on a benzylamine substrate support a reaction mechanism that consists of acetate-assisted C-H bond activation, migratory-insertion, and C-N bond formation steps that involve 28-30 kcalmol-1. The computational study is extended to additional substrates, namely, 1-naphthylmethyl-, 2-methylallyl-, and 2-thiophenemethylamines.

Original languageEnglish (US)
Pages (from-to)8626-8636
Number of pages11
JournalChemistry - A European Journal
Volume21
Issue number23
DOIs
StatePublished - Jun 1 2015

Keywords

  • C-H activation
  • amines
  • density functional calculations
  • nitrogen heterocycles
  • ruthenium

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