Template Catalysis by Metal-Ligand Cooperation. C-C Bond Formation via Conjugate Addition of Non-activated Nitriles under Mild, Base-free Conditions Catalyzed by a Manganese Pincer Complex

Alexander Nerush, Matthias Vogt, Urs Gellrich, Gregory Leitus, Yehoshoa Ben-David, David Milstein

Research output: Contribution to journalArticle

81 Citations (Scopus)

Abstract

The first example of a catalytic Michael addition reaction of non-activated aliphatic nitriles to α,β-unsaturated carbonyl compounds under mild, neutral conditions is reported. A new de-aromatized pyridine-based PNP pincer complex of the Earth-abundant, first-row transition metal manganese serves as the catalyst. The reaction tolerates a variety of nitriles and Michael acceptors with different steric features and acceptor strengths. Mechanistic investigations including temperature-dependent NMR spectroscopy and DFT calculations reveal that the cooperative activation of alkyl nitriles, which leads to the generation of metalated nitrile nucleophile species (α-cyano carbanion analogues), is a key step of the mechanism. The metal center is not directly involved in the catalytic bond formation but rather serves, cooperatively with the ligand, as a template for the substrate activation. This approach of "template catalysis" expands the scope of potential donors for conjugate addition reactions.

Original languageEnglish
Pages (from-to)6985-6997
Number of pages13
JournalJournal of the American Chemical Society
Volume138
Issue number22
DOIs
Publication statusPublished - Jun 8 2016

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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