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Accessing Monomers, Surfactants, and the Queen Bee Substance by Acrylate Cross-Metathesis of Long-Chain Alkenones

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Journal of the American Oil Chemists' Society

Abstract

Polyunsaturated long-chain alkenones are a unique class of lipids biosynthesized in significant quantities (up to 20% of cell carbon) by several algae including the industrially grown marine microalgae Isochrysis. Alkenone structures are characterized by a long linear carbon chain (35–40 carbons) with one to four trans double bonds and terminating in a methyl or ethyl ketone. Alkenones were extracted and isolated from commercially obtained Isochrysis biomass and then subjected to cross-metathesis (CM) with methyl acrylate or acrylic acid using the Hoveyda–Grubbs metathesis initiator. Within 1 h at room temperature alkenones were consumed; however, complete fragmentation (i.e., conversion to the smallest subunits by double bond cleavage) required up to 16 h. Analysis of the reaction mixture by gas chromatography and comprehensive two-dimensional gas chromatography revealed a predictable product mixture consisting primarily of long-chain (mostly C17) acids (or methyl esters from CM with methyl acrylate) and diacids (or diesters), along with smaller amounts (~5%) of the honey bee “queen substance” (E)-9-oxo-decenoic acid. Together, these compounds comprise a diverse mixture of valuable chemicals that includes surfactants, monomers, and an agriculturally relevant bee pheromone.

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Acknowledgements

This work was supported by the National Science Foundation (CHE-1151492) and through a private donation from friends of WHOI.

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Authors and Affiliations

  1. Department of Chemistry, Western Washington University, 516 High Street, Bellingham, WA, 98225, USA

    Gregory W. O’Neil, John R. Williams & Alexander M. Craig

  2. Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, Woods Hole, MA, 02543, USA

    Robert K. Nelson, Kelsey M. Gosselin & Christopher M. Reddy

Authors
  1. Gregory W. O’Neil
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  2. John R. Williams
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Corresponding author

Correspondence to Gregory W. O’Neil.

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Supplementary material GC × GC data (PDF 2273 kb)

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O’Neil, G.W., Williams, J.R., Craig, A.M. et al. Accessing Monomers, Surfactants, and the Queen Bee Substance by Acrylate Cross-Metathesis of Long-Chain Alkenones. J Am Oil Chem Soc 94, 831–840 (2017). https://doi.org/10.1007/s11746-017-2997-8

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  • DOI: https://doi.org/10.1007/s11746-017-2997-8

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