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Issue 29, 2017
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The underlying factors controlling the Pd-catalyzed site-selective alkenylation of aliphatic amines

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Abstract

The Pd(II)-catalyzed site-selective δ-C(sp3)–H alkenylation in the presence of more accessible γ-C(sp3)–H bonds is investigated by DFT calculations. Migratory insertion is found to be both the rate-limiting and the selectivity-determining step. The origin of the unusual site-selectivity is originally attributed to the different steric repulsion between the alkyne and palladacycle; however, our theoretical results reveal that the inherent electronic effect instead of steric repulsion determines the site-selectivity. The proposal is further validated by model calculations involving the less sterically hindered 1,2-dimethyl acetylene and acetylene. In addition, a novel HCO3-assisted N–H activation mechanism is reported, and the origin of the regioselectivity of an unsymmetrical alkyne is also studied.

Graphical abstract: The underlying factors controlling the Pd-catalyzed site-selective alkenylation of aliphatic amines

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Publication details

The article was received on 29 Apr 2017, accepted on 23 Jun 2017 and first published on 26 Jun 2017


Article type: Paper
DOI: 10.1039/C7DT01568B
Citation: Dalton Trans., 2017,46, 9430-9439
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    The underlying factors controlling the Pd-catalyzed site-selective alkenylation of aliphatic amines

    Y. Xing, J. Liu, C. Sun, F. Huang and D. Chen, Dalton Trans., 2017, 46, 9430
    DOI: 10.1039/C7DT01568B

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