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Gold(I)-catalyzed cycloisomerization of ortho-(alkynyl) styrenes: DFT analysis of the crucial role of SbF6 in the elimination of protons

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Abstract

This study reports the first theoretical evidence for the crucial role played by SbF6 in the determination of the regioselectivity in the gold-catalyzed cycloisomerization of ortho-(phenylethynyl) styrenes. According to our calculations, irrespective of using α-substituted or β,β-disubstituted o-(phenylethynyl) styrene, a novel and unusual reaction pathway for elimination of protons involving a four-center-three-electron intermediate, instead of the generation of HSbF6, is observed. On account of the electronic effect, the ring expansion pathway is more favorable than the elimination pathway for α-substituted o-(phenylethynyl) styrene. By using β,β-disubstituted o-(phenylethynyl) styrene, an elimination pathway involving the four-center-three-electron intermediate affords the indenyl derivative. Based on our calculation results and experimental facts, the regioselectivity for the title reaction is mainly controlled by electronic effects rather than steric effects. The theoretical results not only well rationalize the experimental observations but also provide insights into the details of the reaction.

Graphical abstract: Gold(i)-catalyzed cycloisomerization of ortho-(alkynyl) styrenes: DFT analysis of the crucial role of SbF6− in the elimination of protons

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Publication details

The article was received on 20 Feb 2018, accepted on 29 Mar 2018 and first published on 02 Apr 2018


Article type: Paper
DOI: 10.1039/C8CY00367J
Citation: Catal. Sci. Technol., 2018, Advance Article
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    Gold(I)-catalyzed cycloisomerization of ortho-(alkynyl) styrenes: DFT analysis of the crucial role of SbF6 in the elimination of protons

    R. Fang, L. Zhou, P. Tu and L. Yang, Catal. Sci. Technol., 2018, Advance Article , DOI: 10.1039/C8CY00367J

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