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- Title
A Mechanistic Study of Direct Activation of Allylic Alcohols in Palladium Catalyzed Amination Reactions.
- Authors
Yasemin Gumrukcu; de Bruin, Bas; Reek, Joost N. H.
- Abstract
We here report a computational approach on the mechanism of allylicamination reactions using allyl-alcohols and amines as the substrates and phosphoramidite palladium catalyst 1a, which operates in the presence of catalytic amount of 1,3-diethylurea as a co-catalyst. DFT calculations showed a cooperative hydrogen-bonding array between the urea moiety and the hydroxyl group of the allyl alcohol, which strengthens the hydrogen bond between the O-H moiety of the coordinated allyl-alcohol and the carbonyl-moiety of the ligand. This hydrogen bond pattern facilitates the (rate-limiting) C-O oxidative addition step and leads to lower energy isomers throughout the catalytic cycle, clarifying the role of the urea-moiety.
- Subjects
ALCOHOLS (Chemical class); AMINATION; PALLADIUM; CATALYSTS; HYDROGEN bonding
- Publication
Catalysts (2073-4344), 2015, Vol 5, Issue 1, p349
- ISSN
2073-4344
- Publication type
Article
- DOI
10.3390/catal5010349