Abstract
A few lignans, that is, 7-hydroxymatairesinol, secoisolariciresinol, lariciresinol, and nortrachelogenin, predominate in a large proportion of the industrially important softwood species used. Some other lignans, of which some still are unidentified, are also present in lower amounts. Softwood knots, i.e., the branch bases inside tree stems, commonly contain exceptionally large amounts of free aglycone lignans, which has provided a great opportunity to isolate sufficient amounts of softwood lignans for structural characterisation. Here we present the identification and characterisation of two new 9-epimers of 7-hydroxy divanillyl butyrolactol lignans, (7S,8R,8′R,9′R)-4,4′,7-trihydroxy-3,3′-dimethoxylignano-9′,9′-lactol and (7S,8R,8′R,9′S)-4,4′,7-trihydroxy-3,3′-dimethoxylignano-9′,9′-lactol, in knotwood of Colorado spruce (Picea pungens), from tentative GC-MS analysis to final determination of the structure by NMR spectroscopy and X-ray analysis. Further analyses have verified the occurrence of these lignans, which were earlier incorrectly addressed by our group as isomers of liovil, in several spruce, pine, and fir species.
References
Andersson, R., Popoff, T., Theander, O. (1975) A new lignan from Norway spruce. Acta Chem. Scand.B29:835–837.10.3891/acta.chem.scand.29b-0835Search in Google Scholar
Ekman, R. (1976) Analysis of lignans in Norway spruce by combined gas chromatography-mass spectrometry. Holzforschung30:79–85.10.1515/hfsg.1976.30.3.79Search in Google Scholar
Ekman, R. (1979) Distribution of lignans in Norway spruce. Acta Acad. Abo B39:1–6.Search in Google Scholar
Ekman, R., Holmbom, B. (1989a) Analysis by gas chromatography of the wood extractives in pulp and water samples from mechanical pulping of spruce. Nord. Pulp Pap. Res. J.4:16–24.10.3183/npprj-1989-04-01-p016-024Search in Google Scholar
Ekman, R., Holmbom, B. (1989b) The wood extractives in alkaline peroxide bleaching of groundwood from Norway spruce. Nord. Pulp Pap. Res. J.4:188–191.10.3183/npprj-1989-04-03-p188-191Search in Google Scholar
Ekman, R., Willför, S., Sjöholm, R., Reunanen, M., Mäki, J., Lehtilä, R., Eckerman, C. (2002) Identification of the lignan nortrachelogenin in knot and branch heartwood of Scots pine (Pinus sylvestris L.). Holzforschung56:253–256.10.1515/HF.2002.041Search in Google Scholar
Eklund, P., Sillanpää, R., Sjöholm, R. (2002) Synthetic transformation of hydroxymatairesinol from Norway spruce (Picea abies) to 7-hydroxysecoisolariciresinol, (+)-lariciresinol and (+)-cyclolariciresinol. J. Chem. Soc. Perkin Trans. 116:1906–1910.10.1039/B202493DSearch in Google Scholar
Eklund, P.C., Willför, S.M., Smeds, A.I., Sundell, F.J., Sjöholm, R.E., Holmbom, B.R. (2004) A new lariciresinol-type butyrolactone lignan derived from hydroxymatairesinol and its identification in spruce wood. J. Nat. Prod.67:927–931.10.1021/np0340706Search in Google Scholar PubMed
Farrugia, L.J. (1997) ORTEP-3 for Windows – a version of ORTEP-III with a graphical user interface (GUI). J. Appl. Cryst.30:565.10.1107/S0021889897003117Search in Google Scholar
Freudenberg, K., Knof, L. (1957) Die Lignane des Fichtenholzes. Chem. Ber.90:2857–286910.1002/cber.19570901221Search in Google Scholar
Holmbom, B., Eckerman, C., Eklund, P., Hemming, J., Nisula, L., Reunanen, M., Sjöholm, R., Sundberg, A., Sundberg, K., Willför, S. (2003) Knots in trees – a new rich source of lignans. Phytochem. Rev.2:331–340.10.1023/B:PHYT.0000045493.95074.a8Search in Google Scholar
Lindberg, L.E, Willför, S.M., Holmbom, B.R. (2004) Antibacterial effects of knotwood extractives on paper mill bacteria. J. Ind. Microbiol. Biotechnol.31:137–147.10.1007/s10295-004-0132-ySearch in Google Scholar
Miller, R.W., McLaughlin, J.L., Powell, R.G., Plattner, R.D., Weisleder, D., Smith, C.R. Jr. (1982) Lignans from Taxus wallichiana. J. Nat. Prod.45:78–82.10.1021/np50019a007Search in Google Scholar
Omori, S., Ozawa, S., Taneda, K. (1994) The extractives of Aomori Todomatsu (Abies mariesii Masters). Isolations of lignans from the heartwood. Mokuzai Gakkaishi40:1107–1118.Search in Google Scholar
Örså, F., Holmbom, B. (1994) A convenient method for the determination of wood extractives in papermaking process waters and effluents. J. Pulp Pap. Sci.20:J361–J366.Search in Google Scholar
Otwinowski, Z., Minor, W. (1997) Methods in enzymology. In: Macromolecular Crystallography, Part A., Vol. 276. Eds. Carter, C.W. Jr., Sweet R.M. Academic Press, New York. pp. 307–326.Search in Google Scholar
Ozawa, S., Sasaya, T. (1988) Extractives of Todomatsu Abies sachalinensis Masters. V. A novel dibenzylbutyrolactol lignan from the wood of Abies sachalinensis. Mokuzai Gakkaishi34:851–857.Search in Google Scholar
Sasaya, T., Ozawa, S. (1991) Distribution and accumulation of extractives in tree trunk. III. Lignans in the wood of Abies sachalinensis. Enshurin Kenkyu Hokoku48:247–257.Search in Google Scholar
Sheldrick, G.M. SHELXS-97. University of Göttingen, Germany, 1997.Search in Google Scholar
Umezawa, T. (2003) Diversity in lignan biosynthesis. Phytochem. Rev.2:371–390.10.1023/B:PHYT.0000045487.02836.32Search in Google Scholar
Weinges, K. (1960) Die Lignane des Überwallungsharzes der Fichte. Tetrahedron Lett.20:1–2.10.1016/S0040-4039(01)99353-0Search in Google Scholar
Willför, S., Hemming, J., Reunanen, M., Eckerman, C., Holmbom, B. (2003a) Lignans and lipophilic extractives in Norway spruce knots and stemwood. Holzforschung57:27–36.10.1515/HF.2003.005Search in Google Scholar
Willför, S., Hemming, J., Reunanen, M., Holmbom, B. (2000b) Phenolic and lipophilic extractives in Scots pine knots and stemwood. Holzforschung57:359–372.10.1515/HF.2003.054Search in Google Scholar
Willför, S.M., Ahotupa, M.O., Hemming, J.E., Reunanen, M.H.T., Eklund, P.C., Sjöholm, R.E., Eckerman, C., Pohjamo, S.P., Holmbom, B. (2003c) Antioxidant activity of knotwood extractives and phenolic compounds of selected tree species. J. Agric. Food Chem.51:7600–7606.10.1021/jf030445hSearch in Google Scholar PubMed
Willför, S., Nisula, L., Hemming, J., Reunanen, M., Holmbom, B. (2004a) Bioactive phenolic substances in industrially important tree species. Part 1. Knots and stemwood of different spruce species. Holzforschung58:335–344.10.1515/HF.2004.052Search in Google Scholar
Willför, S., Reunanen, M., Eklund, P., Sjöholm, R., Kronberg, L., Fardim, P., Pietarinen, S., Holmbom, B. (2004b) Oligolignans in Norway spruce and Scots pine knots and Norway spruce stemwood. Holzforschung58:345–354.10.1515/HF.2004.053Search in Google Scholar
Willför, S., Nisula, L., Hemming, J., Reunanen, M., Holmbom, B. (2004c) Bioactive phenolic substances in industrially important tree species. Part 2. Knots and stemwood of different fir species. Holzforschung58:650–659.10.1515/HF.2004.119Search in Google Scholar
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