Journal of the American Chemical Society p. 6985 - 6997 (2016)
Update date:2022-08-04
Topics:
Nerush, Alexander
Vogt, Matthias
Gellrich, Urs
Leitus, Gregory
Ben-David, Yehoshoa
Milstein, David
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.
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Doi:10.1016/0008-6215(87)80202-1
(1987)Doi:10.1039/jr9500001505
(1950)Doi:10.1021/jo00830a023
(1970)Doi:10.1002/chem.201402334
(2014)Doi:10.3987/COM-14-S(K)64
(2015)Doi:10.1248/cpb.34.2890
(1986)