Journal article
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
Journal of the American Chemical Society, Vol.138(22), pp.6985-6997
Jun/2016
Abstract
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.
Details
- 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
- Creators
- Alexander Nerush (null) - The Weizmann Institute of ScienceMatthias Vogt (null) - The Weizmann Institute of ScienceUrs Gellrich (null) - The Weizmann Institute of ScienceGregory Leitus (null) - 972WIS_INST___100Yehoshoa Ben-David (null) - The Weizmann Institute of ScienceDavid Milstein (null) - The Weizmann Institute of Science
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.138(22), pp.6985-6997; Jun/2016
- Number of pages
- 13
- Language
- English
- DOI
- https://doi.org/10.1021/jacs.5b13208
- Grant note
- Israel Science Foundation; MINERVA Foundation; Kimmel Center for Molecular Design; Swiss Friends of the Weizmann Institute; DAAD; Feinberg graduate school_ALMAME_DELIMITER_
- Record Identifier
- 993267901603596
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