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Open AccessArticle

A Mechanistic Study of Direct Activation of Allylic Alcohols in Palladium Catalyzed Amination Reactions

Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands
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Academic Editor: Keith Hohn
Catalysts 2015, 5(1), 349-365; https://doi.org/10.3390/catal5010349
Received: 11 December 2014 / Revised: 25 February 2015 / Accepted: 28 February 2015 / Published: 11 March 2015
(This article belongs to the Special Issue Feature Papers to Celebrate the Landmarks of Catalysts)
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. View Full-Text
Keywords: amination; allylic alcohols; palladium; DFT calculations; allylic alkylation amination; allylic alcohols; palladium; DFT calculations; allylic alkylation
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Gumrukcu, Y.; De Bruin, B.; Reek, J.N.H. A Mechanistic Study of Direct Activation of Allylic Alcohols in Palladium Catalyzed Amination Reactions. Catalysts 2015, 5, 349-365.

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