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

Catalysts

Yasemin Gumrukcu²  Bas de Bruin¹  Joost N. H. Reek¹ 

[1] Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands; E-Mail

关键词: amination;    allylic alcohols;    palladium;    DFT calculations;    allylic alkylation;   

DOI  :  10.3390/catal5010349

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2015 by the authors; licensee MDPI, Basel, Switzerland.