Experimental and theoretical mechanistic studies on the Cu(OTf)2-catalyzed hydroamination reaction of terminal allenes with secondary amines reveal that in-situ generated cationic Cu(I) is the catalytically active species and explain the observed regio- and stereoselectivity for the unbranched E product. Insight about the structure of the relevant transition states allowed the generalization of this methodology to allenamides and N-allenylcarbamates under unprecedentedly mild and functional group tolerant conditions. Chelation effect by the amide oxygen in addition to electronic effects explain the high innate reactivity of this class of substrates.
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References:
Copper-Catalyzed Hydroamination of Allenes: from Mechanistic Understanding to Methodology Development
Luca Alessandro Perego, Rémi Blieck, Antoine Groué, Florian Monnier, Marc Taillefer, Ilaria Ciofini*, Laurence Grimaud*
ACS Catalysis, 2017, 7 (7), pp 4253–4264
DOI: 10.1021/acscatal.7b00911
Copper-Catalyzed Hydroamination of Allenes: from Mechanistic Understanding to Methodology Development