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Ferulate–coniferyl alcohol cross-coupled products formed by radical coupling reactions

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Abstract

Radical coupling reactions between ethyl ferulate (Et-FA), a simple model for feruloyl polysaccharides in planta, and coniferyl alcohol (CA), a monolignol, were studied in order to better understand the polymer cross-coupling interactions among polysaccharides and monolignols or lignin, mediated by ferulate (FA), in plant cell walls. Cross-coupled FA/CA dimers produced in an aqueous buffer (pH 5.0) containing peroxidase/hydrogen peroxide were isolated and characterized by NMR. The total coupling products were characterized by 2D 13C–1H correlation (HSQC) NMR spectroscopy and GC–MS. Results from this study showed that ferulate readily cross-couples with coniferyl alcohol through free radical coupling mechanisms producing a series of cross-coupled FA/CA dimers with β-O-4-, β-5-/8-5-, and 8-β-linkages; the syntheses and isolation of β-5- and 8-5-cross-coupled dimers are reported here. The transformation from 8-β-coupled FA/CA hydroxyl esters into lactones through intramolecular transesterification is demonstrated for the first time and mechanisms behind these transformations are discussed. The finding of both β-5- and 8-5-cross-coupled dimers in this study suggests that analogs of both may be present in plant cell walls. Finally it is suggested that ferulates in plants indeed react with monolignols through free radical mechanisms producing a more diverse array of cross-coupled dimers than previously reported.

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Abbreviations

FA:

Ferulate

CA:

Coniferyl alcohol

Et-FA:

Ethyl ferulate

NMR:

Nuclear magnetic resonance (spectroscopy)

HSQC:

Heteronuclear single quantum correlation (spectroscopy)

COSY:

Correlation spectroscopy

TMS:

Trimethylsilylation

TLC:

Thin layer chromatography

DHP:

Dehydrogenation polymer (synthetic lignin)

TIC:

Total-ion chromatography

GC–MS:

Gas chromatography–mass spectrometry

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Acknowledgments

The authors would like to thank the US Dairy Forage Research Center for access to the AMX-360 NMR and Shimadzu GCMS-QP 2010 instrumentation that was essential to this work. We are also grateful to the China Scholarship Committee, State Education Department for supporting Aiping Zhang as a visiting scholar in the Department of Biochemistry, University of Wisconsin, and at the US Dairy Forage Research Center.

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Authors and Affiliations

  1. Department of Biochemistry (Enzyme Institute), and the Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, 1710 University Avenue, Madison, WI, 53726, USA

    Aiping Zhang, Fachuang Lu & John Ralph

  2. State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, 510641, Guangzhou, China

    Aiping Zhang & Runcang Sun

Authors
  1. Aiping Zhang
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  2. Fachuang Lu
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  3. Runcang Sun
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  4. John Ralph
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Correspondence to Fachuang Lu.

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Zhang, A., Lu, F., Sun, R. et al. Ferulate–coniferyl alcohol cross-coupled products formed by radical coupling reactions. Planta 229, 1099–1108 (2009). https://doi.org/10.1007/s00425-009-0894-6

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  • DOI: https://doi.org/10.1007/s00425-009-0894-6

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