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Implications of Active Intermediate and Olefin Attachment Position in the Piperine Metathesis

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Abstract

First and second generation of Grubbs catalysts (G1 and G2) were applied in the piperine olefin metathesis under different conditions. G1 was used in self-metathesis, G2 was implemented in both, self and cross-metathesis of piperine with eugenol. Results allowed to implicate about the main intermediate of the reaction and the position of olefin attachment to the catalyst, assuming that the reaction follows a pathway where 2A=B olefin leads to the formation of A=A and B=B. In addition, the results contributed to the studies of catalyst’s reactivity when the olefin metathesis product required the high electronic effect of the N-heterocyclic of G2. In this paper, the highest activity of G2 in the olefin metathesis of eugenol was observed when the first intermediate was Ru-eugenol-moiety in the cross-metathesis of the piperine with eugenol. This demonstrates that the acidity of the new carbene in the intermediate species causes inactivity only in the reaction with piperine.

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Funding

This work was supported by CAPES (Higher Education Personnel Improvement Coordination), FAPEPI (Research Support Foundation of the State of Piauí) (Notice 06/2018 FAPEPI/CAPES), and the State University of Piauí (UESPI) and the Research Laboratory—Generation of New Technologies − GERATEC. In addition, we would like to thank the Institute of Chemistry São Carlos for the 1H NMR spectra.

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Authors and Affiliations

  1. Departamento de Química, Universidade Federal do Piauí, Campus Universitário Ministro Petrônio Portella, 64049-550, Ininga, Teresina, PI, Brazil

    Aline A. C. França & José M. Elias de Matos

  2. Instituto de Química de São Carlos, Universidade de São Paulo, 13560-970, São Carlos, SP, Brazil

    Eliada A. da Silva & Benedito S. Lima-Neto

  3. Faculdade de Ciências e Tecnologia, UNESP – Univ. Estadual Paulista, 19060-900, Presidente Prudente, SP, CEP, Brazil

    Valdemiro P. de Carvalho Júnior

  4. Centro de Ciências da Natureza, Universidade Estadual do Piauí, 64002-150, Teresina, PI, Brazil

    José L. da Silva Sá

Authors
  1. Aline A. C. França
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  2. Eliada A. da Silva
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  3. Benedito S. Lima-Neto
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  4. Valdemiro P. de Carvalho Júnior
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  5. José M. Elias de Matos
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  6. José L. da Silva Sá
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Corresponding authors

Correspondence to José M. Elias de Matos or José L. da Silva Sá.

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Additional information

Abbreviations and notation: G1 and G2, first and second generation of Grubbs catalysts; PCy3, tricyclohexylphosphine; GC–MS, gas chromatography–mass spectrometry; 1H NMR, proton nuclear magnetic resonance.

APPENDIX

APPENDIX

The supporting information iin Appendix ncludes chromatogram cross-metathesis of piperine with eugenol and piperine with cinnamyl alcohol, with G2 as catalyst and chromatogram of use additives SnCl2, CuCl2 and perhydroazepine in olefin metathesis with G1.

Fig. A1.
figure 6

Proposed structures and fragmentation mechanism of Dimer 1.

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Fig. A2.
figure 7

Chromatogram from piperine cross-metathesis with eugenol (A) and piperine with cinnamyl alcohol, (B) with G2 as catalyst. Catalyst:substrate ratio was 1 : 1 mol, reaction time 48 h at 50°C. PCy3 (tricyclohexylphosphine); O=PCy3 (tricyclohexylphosphine oxidized).

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Fig. A3.
figure 8

Chromatogram from piperine metathesis with G2: catalyst:substrate ratio 1 : 100 mol, 48 h, 50°C.

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Fig. A4.
figure 9

Proposed structures and fragmentation mechanism of isopiperine.

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Fig. A5.
figure 10

Chromatogram from piperine olefin metathesis with G1 using additives SnCl2 (A), CuCl2 (B), (C) perhydroazepine and 1,4-benzoquinone (D). Catalyst : substrate ratio 1 : 10 mol, 48 h 50°C. PCy3 (tricyclohexylphosphine); O=PCy3 (tricyclohexylphosphine oxidized), Iso-Pip (isopiperine).

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França, A., da Silva, E.A., Lima-Neto, B.S. et al. Implications of Active Intermediate and Olefin Attachment Position in the Piperine Metathesis. Kinet Catal 64, 783–792 (2023). https://doi.org/10.1134/S0023158423060058

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