Mechanistic Study on Pd/Mono-N-protected Amino Acid Catalyzed Vinyl–Vinyl Coupling Reactions: Reactivity and E/Z Selectivity

A combined mass spectrometric and computational study of the Pd/mono-N-protected amino acid (MPAA)-catalyzed vinyl–vinyl coupling reactions is reported. Computational study reveals that the reaction is initiated by C–H activation of the styrene followed by the insertion of acrylate. This is supporte...

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Bibliographic Details
Published in:Organic letters 2016-10, Vol.18 (20), p.5240-5243
Main Authors: Zhong, Xiu-Mei, Cheng, Gui-Juan, Chen, Ping, Zhang, Xinhao, Wu, Yun-Dong
Format: Article
Language:English
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Summary:A combined mass spectrometric and computational study of the Pd/mono-N-protected amino acid (MPAA)-catalyzed vinyl–vinyl coupling reactions is reported. Computational study reveals that the reaction is initiated by C–H activation of the styrene followed by the insertion of acrylate. This is supported by mass spectrometry. The MPAA ligand facilitates the cross-coupling reaction between monosubstituted alkenes by stabilizing the active palladium catalyst and offering the N-protecting group as a stronger base than acetate. The E/Z selectivity is attributed to the stronger d−π interaction between the catalyst and the substrate in the transition state leading to E product.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.6b02542