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

74 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

Fingerprint

Nitriles
Addition reactions
Manganese
Catalysis
Metals
Chemical activation
Ligands
Carbonyl compounds
Nucleophiles
Discrete Fourier transforms
Pyridine
Nuclear magnetic resonance spectroscopy
Transition metals
Earth (planet)
Catalysts
Substrates
Magnetic Resonance Spectroscopy
Temperature

ASJC Scopus subject areas

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

Cite this

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

In: Journal of the American Chemical Society, Vol. 138, No. 22, 08.06.2016, p. 6985-6997.

Research output: Contribution to journalArticle

@article{de31c7fa8cf7417081ae0e43324722ec,
title = "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",
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.",
author = "Alexander Nerush and Matthias Vogt and Urs Gellrich and Gregory Leitus and Yehoshoa Ben-David and David Milstein",
year = "2016",
month = "6",
day = "8",
doi = "10.1021/jacs.5b13208",
language = "English",
volume = "138",
pages = "6985--6997",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "22",

}

TY - JOUR

T1 - 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

AU - Nerush, Alexander

AU - Vogt, Matthias

AU - Gellrich, Urs

AU - Leitus, Gregory

AU - Ben-David, Yehoshoa

AU - Milstein, David

PY - 2016/6/8

Y1 - 2016/6/8

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84974628545&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84974628545&partnerID=8YFLogxK

U2 - 10.1021/jacs.5b13208

DO - 10.1021/jacs.5b13208

M3 - Article

VL - 138

SP - 6985

EP - 6997

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 22

ER -