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Geranylgeraniol and geranylgeraniol-derived diterpenes from the brown alga Bifurcaria bifurcata (Cystoseiraceae)
Biochemical Systematics and Ecology 27 (1999) 665}668
Short Communication
Geranylgeraniol and geranylgeraniol-derived diterpenes from the brown alga Bifurcaria bifurcata (Cystoseiraceae) GeH rald Culioli , VeH ronique Mesguiche, Louis Piovetti *, Robert Valls Laboratoire de Recherche en Chimie Marine des Organome& talliques (RCMO), Universite& de Toulon et du Var, BP 132, F-83957 La Garde cedex, France Laboratoire des Organo-Phosphore& s, Universite& d+Aix-Marseille III, BP 552, F-13397 Marseille cedex 13, France Received 23 September 1998; received in revised form 11 November 1998; accepted 11 November 1998 Keywords: Cystoseiraceae; Bifurcaria bifurcata; Geranylgeraniol; Linear diterpenes; Chemotaxonomy
1. Subject and source The algal family Cystoseiraceae (order Fucales, class Phaeophyceae) contains a major genus, Cystoseira, with numerous species (57) in the Mediterranean and contiguous Atlantic marine environments (Ribera et al., 1992). In contrast, Bifurcaria is a minor genus with three species: B. galapagensis occurring in equatorial environments (Galapagos islands), B. bifurcata found o! the Atlantic coasts from Morocco (southern limit) to Great Britain (northern limit) and B. brassicaeformis endemic to South Africa (Nizamuddin, 1970). From a chemotaxonomic point of view we have now re-investigated the lipid extract from Bifurcaria bifurcata (Velley) Ross, collected o! the French and Moroccan Atlantic coasts. Voucher specimens of this species [P143.6 (Quiberon), P206.7 (Rosco! ), P192.7 (El Jadida)] are deposited in the Herbarium of Dr. Pellegrini, Laboratoire de Biologie Marine Fondamentale et AppliqueH e, University of Marseille II, France.
*Corresponding author. Tel.: 00 33 4 94 14 23 46; fax: 00 33 4 94 14 21 68; e-mail: [email protected] 0305-1978/99/$ - see front matter 1999 Elsevier Science Ltd. All rights reserved. PII: S0 30 5 - 19 7 8( 9 8 )00 1 26 -4
666
G. Culioli et al./Biochemical Systematics and Ecology 27 (1999) 665}668
2. Previous work Previous studies on the secondary metabolites from the lipid extract from B. bifurcata have shown that this species contains a rich array of linear diterpenes (Biard et al., 1980a, b; Combaut and Piovetti, 1983; Hougaard et al., 1991; Semmak et al., 1988; Valls et al., 1986, 1992a, b, 1993a, b, 1995). These compounds are geranylgeraniol-derived diterpenes such as eleganolone (1) and eleganediol (2). The precursor of these compounds, geranylgeraniol (3), occurs in two brown algae of the genus Cystoseira: C. brachycarpa (Amico et al., 1980), initially mistakenly called C. crinita, and C. balearica (Amico et al., 1987) but it has not been isolated from the genus Bifurcaria until today.
3. Present study The ether extracts of dried Bifurcaria bifurcata collected at three separate locations } Quiberon, Rosco! (Brittany) and El Jadida (Morocco) } were re-investigated to study the minor lipophilic secondary metabolites. The extracts were separately fractionated by liquid chromatography using silica gel; HPLC of the less polar fraction revealed the presence of minor components, in addition to sterols and previously described linear diterpenes. They were subsequently isolated and puri"ed by semi-preparative normal-phase HPLC (EtOAc-isooctane, 1 : 1), leading to 25 mg of pure geranylgeraniol (3) (0.01% of algal dry weight) for the specimens collected at Quiberon and Rosco!, respectively, 120 mg of eleganolal (4) (0.12% of algal dry weight) and 75 mg of isoeleganolal (5) (0.08% of algal dry weight) for the specimen collected at El Jadida. Their structures have been established by means of spectral methods (IR, MS, NMR) and comparison with the literature data (Amico et al., 1987) and with those of a commercial sample for geranylgeraniol.
4. Chemotaxonomic signi5cance Although the compounds 3}5 were known metabolites, they were isolated for the "rst time from B. bifurcata. The presence of geranylgeraniol (3) in this alga suggests that this compound is the precursor of the linear diterpenes previously described. Eleganolal (4) and isoeleganolal (5) have been previously isolated from Cystoseira balearica (Amico et al., 1987). They are oxidation derivatives from eleganolone (1). Moreover, in the course of this work, we have identi"ed eleganolone (1) as a minor constituent of the ether extract from B. bifurcata collected at Rosco!. This compound } not obtained in our previous study of this extract (Valls et al., 1995) } but widely present in extracts from other locations (Biard et al., 1980a, b; Valls et al., 1993a, b), can be regarded as a chemotaxonomic marker of the species.
G. Culioli et al./Biochemical Systematics and Ecology 27 (1999) 665}668
667
668
G. Culioli et al./Biochemical Systematics and Ecology 27 (1999) 665}668
Acknowledgements The authors wish to thank Dr. M. Marron (Centre de Biologie Marine de Rosco!, France), Mr. C. Le Hena! (Algues Marines, Quiberon, France), and Pr S. Bakkas (University of El Jadida, Morocco) for identi"cation and collection of plant material from Rosco!, Quiberon and El Jadida, respectively.
References Amico, V., Oriente, G., Piattelli, M., Ruberto, G., Tringali, C., 1980. Phytochemistry 19, 2759. Amico, V., Neri, P., Piattelli, M., Ruberto, G., 1987. Phytochemistry 26, 2637. Biard, J.F., Verbist, J.F., Floch, R., Letourneux, Y., 1980a. Tetrahedron Lett. 21, 1849. Biard, J.F., Verbist, J.F., Letourneux, Y., Floch, R., 1980b. Planta Medica 40, 288. Combaut, G., Piovetti, L., 1983. Phytochemistry 22, 1787. Hougaard, L., Anthoni, U., Christophersen, C., Nielsen, P.H., 1991. Phytochemistry 30, 3049. Nizamuddin, M., 1970. Bot. Mar. 13, 131. Ribera, M., Gomez Garreta, A., Gallardo, T., Cormaci, M., Furnari, G., Giaccone, G., 1992. Bot. Mar. 35, 109. Semmak, L., Zerzouf, A., Valls, R., Banaigs, B., Jeanty, G., Francisco, C., 1988. Phytochemistry 27, 2347. Valls, R., Banaigs, B., Francisco, C., Codomier, L., Cave, A., 1986. Phytochemistry 25, 751. Valls, R., Banaigs, B., Piovetti, L., Zerzouf, A., 1992a. Oceanis 18, 223. Valls, R., Piovetti, L., Zerzouf, A., Semmak, L., Pei!er, G., 1992b. Cryptogamie Algol. 13, 154. Valls, R., Banaigs, B., Piovetti, L., Archavlis, A., Artaud, J., 1993a. Phytochemistry 34, 1585. Valls, R., Banaigs, B., Piovetti, L., Zerzouf, A., 1993b. An. Inst. Oceanogr. 69, 215. Valls, R., Piovetti, L., Banaigs, B., Archavlis, A., Pellegrini, M., 1995. Phytochemistry 39, 145.
Short Communication
Geranylgeraniol and geranylgeraniol-derived diterpenes from the brown alga Bifurcaria bifurcata (Cystoseiraceae) GeH rald Culioli , VeH ronique Mesguiche, Louis Piovetti *, Robert Valls Laboratoire de Recherche en Chimie Marine des Organome& talliques (RCMO), Universite& de Toulon et du Var, BP 132, F-83957 La Garde cedex, France Laboratoire des Organo-Phosphore& s, Universite& d+Aix-Marseille III, BP 552, F-13397 Marseille cedex 13, France Received 23 September 1998; received in revised form 11 November 1998; accepted 11 November 1998 Keywords: Cystoseiraceae; Bifurcaria bifurcata; Geranylgeraniol; Linear diterpenes; Chemotaxonomy
1. Subject and source The algal family Cystoseiraceae (order Fucales, class Phaeophyceae) contains a major genus, Cystoseira, with numerous species (57) in the Mediterranean and contiguous Atlantic marine environments (Ribera et al., 1992). In contrast, Bifurcaria is a minor genus with three species: B. galapagensis occurring in equatorial environments (Galapagos islands), B. bifurcata found o! the Atlantic coasts from Morocco (southern limit) to Great Britain (northern limit) and B. brassicaeformis endemic to South Africa (Nizamuddin, 1970). From a chemotaxonomic point of view we have now re-investigated the lipid extract from Bifurcaria bifurcata (Velley) Ross, collected o! the French and Moroccan Atlantic coasts. Voucher specimens of this species [P143.6 (Quiberon), P206.7 (Rosco! ), P192.7 (El Jadida)] are deposited in the Herbarium of Dr. Pellegrini, Laboratoire de Biologie Marine Fondamentale et AppliqueH e, University of Marseille II, France.
*Corresponding author. Tel.: 00 33 4 94 14 23 46; fax: 00 33 4 94 14 21 68; e-mail: [email protected] 0305-1978/99/$ - see front matter 1999 Elsevier Science Ltd. All rights reserved. PII: S0 30 5 - 19 7 8( 9 8 )00 1 26 -4
666
G. Culioli et al./Biochemical Systematics and Ecology 27 (1999) 665}668
2. Previous work Previous studies on the secondary metabolites from the lipid extract from B. bifurcata have shown that this species contains a rich array of linear diterpenes (Biard et al., 1980a, b; Combaut and Piovetti, 1983; Hougaard et al., 1991; Semmak et al., 1988; Valls et al., 1986, 1992a, b, 1993a, b, 1995). These compounds are geranylgeraniol-derived diterpenes such as eleganolone (1) and eleganediol (2). The precursor of these compounds, geranylgeraniol (3), occurs in two brown algae of the genus Cystoseira: C. brachycarpa (Amico et al., 1980), initially mistakenly called C. crinita, and C. balearica (Amico et al., 1987) but it has not been isolated from the genus Bifurcaria until today.
3. Present study The ether extracts of dried Bifurcaria bifurcata collected at three separate locations } Quiberon, Rosco! (Brittany) and El Jadida (Morocco) } were re-investigated to study the minor lipophilic secondary metabolites. The extracts were separately fractionated by liquid chromatography using silica gel; HPLC of the less polar fraction revealed the presence of minor components, in addition to sterols and previously described linear diterpenes. They were subsequently isolated and puri"ed by semi-preparative normal-phase HPLC (EtOAc-isooctane, 1 : 1), leading to 25 mg of pure geranylgeraniol (3) (0.01% of algal dry weight) for the specimens collected at Quiberon and Rosco!, respectively, 120 mg of eleganolal (4) (0.12% of algal dry weight) and 75 mg of isoeleganolal (5) (0.08% of algal dry weight) for the specimen collected at El Jadida. Their structures have been established by means of spectral methods (IR, MS, NMR) and comparison with the literature data (Amico et al., 1987) and with those of a commercial sample for geranylgeraniol.
4. Chemotaxonomic signi5cance Although the compounds 3}5 were known metabolites, they were isolated for the "rst time from B. bifurcata. The presence of geranylgeraniol (3) in this alga suggests that this compound is the precursor of the linear diterpenes previously described. Eleganolal (4) and isoeleganolal (5) have been previously isolated from Cystoseira balearica (Amico et al., 1987). They are oxidation derivatives from eleganolone (1). Moreover, in the course of this work, we have identi"ed eleganolone (1) as a minor constituent of the ether extract from B. bifurcata collected at Rosco!. This compound } not obtained in our previous study of this extract (Valls et al., 1995) } but widely present in extracts from other locations (Biard et al., 1980a, b; Valls et al., 1993a, b), can be regarded as a chemotaxonomic marker of the species.
G. Culioli et al./Biochemical Systematics and Ecology 27 (1999) 665}668
667
668
G. Culioli et al./Biochemical Systematics and Ecology 27 (1999) 665}668
Acknowledgements The authors wish to thank Dr. M. Marron (Centre de Biologie Marine de Rosco!, France), Mr. C. Le Hena! (Algues Marines, Quiberon, France), and Pr S. Bakkas (University of El Jadida, Morocco) for identi"cation and collection of plant material from Rosco!, Quiberon and El Jadida, respectively.
References Amico, V., Oriente, G., Piattelli, M., Ruberto, G., Tringali, C., 1980. Phytochemistry 19, 2759. Amico, V., Neri, P., Piattelli, M., Ruberto, G., 1987. Phytochemistry 26, 2637. Biard, J.F., Verbist, J.F., Floch, R., Letourneux, Y., 1980a. Tetrahedron Lett. 21, 1849. Biard, J.F., Verbist, J.F., Letourneux, Y., Floch, R., 1980b. Planta Medica 40, 288. Combaut, G., Piovetti, L., 1983. Phytochemistry 22, 1787. Hougaard, L., Anthoni, U., Christophersen, C., Nielsen, P.H., 1991. Phytochemistry 30, 3049. Nizamuddin, M., 1970. Bot. Mar. 13, 131. Ribera, M., Gomez Garreta, A., Gallardo, T., Cormaci, M., Furnari, G., Giaccone, G., 1992. Bot. Mar. 35, 109. Semmak, L., Zerzouf, A., Valls, R., Banaigs, B., Jeanty, G., Francisco, C., 1988. Phytochemistry 27, 2347. Valls, R., Banaigs, B., Francisco, C., Codomier, L., Cave, A., 1986. Phytochemistry 25, 751. Valls, R., Banaigs, B., Piovetti, L., Zerzouf, A., 1992a. Oceanis 18, 223. Valls, R., Piovetti, L., Zerzouf, A., Semmak, L., Pei!er, G., 1992b. Cryptogamie Algol. 13, 154. Valls, R., Banaigs, B., Piovetti, L., Archavlis, A., Artaud, J., 1993a. Phytochemistry 34, 1585. Valls, R., Banaigs, B., Piovetti, L., Zerzouf, A., 1993b. An. Inst. Oceanogr. 69, 215. Valls, R., Piovetti, L., Banaigs, B., Archavlis, A., Pellegrini, M., 1995. Phytochemistry 39, 145.