Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 22, Pages 6985-6997Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b13208
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Funding
- Israel Science Foundation
- MINERVA Foundation
- Kimmel Center for Molecular Design
- Swiss Friends of the Weizmann Institute
- DAAD
- Feinberg graduate school
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The first example of a catalytic Michael addition reaction of non activated aliphatic nitriles to alpha,beta-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 (alpha-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.
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