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Jasmonic Acid and Coronatin Induce Odor Production in Plants.

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[15] Deprotection was carried out after macrocyclization because of problems with
furan formation during Glaser- Hay coupling with (R)-(
-)-I9 It seems that
2-alkynylphenols are stable under neutral and mildly basic conditions. but are
more likely to form furans under strongly acidic or basic conditions: see: a)
C. E. Castro. E . J. Gaughan. D. C. Owsley. J. Org. U i m . 1966,3/,4071 -4078;
h) S. Torii, L. H Xu. H. Okumoto, Swilerr. 1992, 515-516.
[I61 CDCI, was allowed to stand over anhydrous K,CO, for at least 24 h prior to
use in tirrations. Remaining water was removed by the addition ofjust cnough
powdered molecular sieves (4 A) to the NMR tube to make the water peak a t
d = 1.54 disappear: see ref. [51].
[I71 Associate V. 1.6, Blake Peterson, Ph.D. thesis. UCLA 1994.
[I81 C.-Y. Huang. L. A. Cabell. E. V. Anslyn. J. A m . Cheni. Soc. 1994, 116. 27782792.
[I91 Y. Kikuchi, H. Toi, Y Aoyama. Bull. Chnn. Suc. Jpn. 1993. 66. 1856- 1858.
[20] R. N. Keller. H. D. Wycoff in Inorganic Synrhesr.~.&J/.2 (Ed.: W. C. Fernelius), McGraw Hill. New York, 1946, pp. 1-4.
Jasmonic Acid and Coronatin Induce
Odor Production in Plants
Wilhelm Boland,* Jorn Hopke, Jens D o n a t h ,
Jorg N u s k e , and Friedemann Bublitz
Dedicated to Professor Dieter G. Miillev
on the occasion of his 60th birthday
Jasmonic acid (JA) and certain derivatives (e.g. methyl jasmonate, JA-Me) play a key role as phytohormones, elicitors,
and signal transducers.['] They are formed from linolenic acid
through a known sequence of reactions (Scheme 1)[21and induce
the expression of specific genes in the form of proteins (Jasmonate Induced Proteins, JIPs),c31 which are responsible for a
number of effects including defoliation, senescence promotion,['] and emission of ethylene.c51Similar, adverse results can
be induced by application of the structurally related phytotoxin
coronatin, which has been previously isolated from culture filtrates of pathogenic strains of Pseudomonas syringae[6' and
Xanrhomonas cnmpe~trir."~Again, the typical effects are
chlorose, senescence, and enhanced ethylene
In recent years JA has been found to stimulate a number of
other effects. Among them, tomato tuber induction,['] tendril
coiling,[lo1and the induction of secondary metabolite biosynthesis" in cell suspension cultures of Esclioltzia calfornica and
Rauvo@u canescens are particularly noteworthy. Again. similar
effects can be triggered by coronatin.["] Moreover, J A and JAMe appear to be important stress signals, or signal transducers,
in plants' defense against herbivores, since both induce the
biosynthesis of proteinase inhibitors.[l3,''I Plant defense also
involves the release of volatile substances which may act inter
alia as intra- or interspecific "SOS
attracting predators that prey on herbivore^.^'^^''^
We report here that the biosynthesis and emission of volatiles
can be triggered in many plant species by application of J A and
coronatin. The effect is demonstrated in Figure 1 for Nicotiana
tabacum. Leaves from untreated tobacco plants release volatiles
1
looA
1
linolenic acid
8
I
coronatin
\
500
fl-
0
Fig. 1. Gas chromatographic analysis of volatiles from tobacco leaves (Nicoticcnu
rohucuin) A ) untreated, B) after treatment with jasmonic acid. The relative signal
intensity I is plotted against the number t i of the scan ( I scan per second). Compounds identified: neophytadiene ( I ) . C2,,H3> 2. (3Z)-hex-3-enyl acetate (3), oct-len-3-ol (4). indole (5). (3Z)-hex-3-enyl tiglate (6). /klemene (7). (3Z)-hex-3-cnyl
benzoate (8). 4,8.1?-triinethyltrideca-l.3.7.1I-tetraene (9).
0.
jasmonic acid (JA) R = H
epijasmonic acid
JA-Me, R = CH3
Scheme 1. Synthesis ofjasmonic acid and methyl jasmonatr from linolenic acid and
the structure of coronatin
["I
Prof. Dr. W. Boland. Dipl.-Chem J. Hopke, Dr. J. Donath
lnstitut fur Organische Chemie und Biochemie der Universitit
Gerhard-Domagk-Strasse 1, D-53121 Bonn (Germany)
Telefax. Int. code (228)735388
Dr. J. Niiskc, Dr. F. Buhlitz
Institut fur Mikrohiologie der Universitit Jena (Germany)
[**I Herbivore-Induced Volatiles, Part 2. This work was supported by the Dsutsche
Forschungsgemeinschaft and by the Fonds der Chemischen Industrie. We
thank Dr R. Kaiser. Givaudan Company (Diibendorf, Switzerland). for samples of methyl jasmonate. Part 1 : ]ref. [I 81.
+
at relatively low levels (Fig. 1 A). However, following 30 h of
incubation with JA (10 pmolmL- l), supplied through the petiole of a freshly detached leaf, a dramatic increase in the production of a number of volatiles is seen (Fig. 1 B). The effect can still
be triggered with roughly 100 ninolmL- ofJA. An overview of
the JA-treated plants, the type of volatiles produced, and the
extent to which individual compounds or compound classes are
triggered is presented in Table 1. As previously shown for
Plzaseolus lunutus (lima bean) and Zea mays (maize), the maximum rate of volatile emission is reached within 20-30 h after
application of JA.C1*]The volatile substances released can be
divided into three classes of compounds: 1) mevalogenins,
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Xihlc 1 Sciiiiqii;in~iiati\rcoinpilation of volatiles from selected plants after treatment with jasmonlc acid [a].
Terpene\
(h)-/j-ocirnene
-I-
010
ili
010
-I-
.I-
-I-
-/+
-I-
-10
+It
ol+
-I++
-/-
-I-
-lo
Ibl
-1.
-I-
+I+
CiOHl4 I L I
nerolidol
-1-
-I-
o/i
-1-
ol+
-1.
01-
CI,H*,Idl
B-caryophyllene
-I-
o/+
-1-
o/+
-1-
-I+
+I++
additional monoterpenes
+It
010
++I+++*
additional sesquiterpenes
010
diterpenes
-I-
o/+
-1-
-1-
(3Q-hex-3-envl acetate
+I+
o/+
-I-
-1ol++
-10
I -octen-3-01
-1-
-1-
-1-
-I-
010
+/+
-I-I-
linalool
CiiHI8
+I**
*I*
+I*
-I+
ol+
-/*
-1-
-1-
.I-
-I-
-/-
./.
-I-
-10
Oltt
-lo
-1-
-1-
o/+
-I-
-I+
-1.
01-
o/i
01%
-lo
-I-
-/i
-/++
-I-
010
ol+
010
-I-
OI-CH'
Ol++t*
++I**
+I**
Ol**
O/*
-I+
-1-
i/*
010
-I-
-I-
+I+*
-/-
-10
-/+
-I-
-I-
01010
-I-
+I+
-lo
ol+
-1-
ol+
ol++
o/+
01-
010
-I++
-I-
o/++
OI**
-/*
-I-
-1-
-/++
010
-10
-I-
-I-
-1-
-/-
+/+
o/+
+lo
-I+
-1-
-1-
-I-
-lo
-1.
-I+
-lo
-lo
-I+
-10
-I+
010
-I-
-1-
-1-
-I+
-/+
o/+
-/+
-I-
-I++
-I+
-I-
-I*
-/-
010
4-
Acetopenins
additional acetogenins
+tt/+*I
Arenes
benzyl alcohol
-I-
-1-
-1-
methyl salicylate
-/-
-\-
-/-
indole
-/++
-1-
-/-
-I-
-I++
-I-
oli
-I-1-
-I-
-[-
-/*
-I+
additional arenes
rnethvl ismonate
-
010
-I-
-/*
-/*
-/*
-It
o/+
-I**
~-
+
++
+++
Designation?. (untreatcd.'treated with jasmonic acid): -: not present, o : < 5 % .
: 0.5-5%.
: 5-25%.
: >?~YO.
* inam component of the mixture. The percentages are calculated relative to the inajor component in the chromatogram [b] 4.8Diinethq Inona- I 3.7-trienc. [c] Monoterpene. [d] 4.8,12-Tnmethyltrideca-l.3.7.11 -tetraem
[hi]
mainly mono- and sesquiterpenes; 2) acetogenins, degradation
products of fatty acid hydroperoxides (e.g. esters of leaf alcohols
and oct-1 -enc-3-ol): 3) aromatic compounds (alcohols, esters,
and indole).
While the leaves of most plants show significant characteristics of senescence (withering, browning along the vascular bundles) after treatment with J A ( > 10 pmol mL- ')- similar adverse
effects failed to appear after treatment with coronatin (50 and
100 nmolmL - I ) . Experiments were carried out with the lima
bean ( P . lunuti~s)
and maize ( Z .mays) as two typical representatives of mono- and dicotyledonous plants. In general, coronatin
proved to be the superior inducing agent; the threshold concentration for odor induction was roughly 1 n m o l m l - I . The pattern of the induced volatiles corresponds to that from treatment
with JA, but owing to the low concentrations of coronatin used
(50 and 100 nmolmL-') no senescence promotion was observed.
Strong odor induction by JA in the fern Dr-vopteris
fi'li.~mci.c.indicates that this signal transduction pathway may
be an archetypal development within the phylogeny of
plants. which apparently persists even in modern dicotyledonous plants like i\i. tubacutn and P. lunatus. This is also supported by JA induction of volatiles in the leaves of the pharmacologically interesting gingko tree (Ginkgo hiloba), the last
representative of the genus Ginkoopsida. Leaves of the willow
tree (.Tali.\- dim) likewise release volatiles after treatment
with JA.
I t must be emphasized. however. that the application of J A
does not always result in the production and emission of novel
compounds; in several cases only the relative composition of the
mixture of volatiles is altered (Table 1, Brcissica oleraceu, Eucaljptxv g l c h u l i r . ~ ) It
. remains to be established whether the pro-
duction of volatiles is due to activation of the defense genes
within the various plants, or if it is a concomitant effect of
senescence. Irrespective of the signaling pathway within the
plant, it is interesting to see that the JA- or coronatin-induced
volatiles from the lima bean ( P . lunutus) and maize ( Z . mays)
correspond to those typically released in response to an attacking herbivore."
'*]
The emission of methyl jasmonate (JA-Me) from some of the
JA-treated plants (cf. Table 1) appears significant, since gaseous
JA-Me has been shown to induce defense reactions in neighboring plants like, for example, the synthesis of proteinase inh i b i t o r ~ [ 'and
~ ] p h y t o a l e x i n ~ . [ ~In
~ ~this
' ~ ] respect. the emission
of JA-Me may be taken as additional evidence for the involvement of volatile jasmonates in interplant communication. In a
similar fashion volatile methyl salicylate (Table 1, P . hmarus)
may activate defense genes,['O1 but this effect still remains to be
established.
Odor induction by JA and coronatin provides interesting perspectives. Since the biosynthesis of most of the volatile compounds in Table 1 is known. their detection after JA or coronatin treatment should allow preliminary extrapolations to the
enzymatic level and may provide valuable hints for the identification of still unknown JIPs. Other interesting applications may
include the attraction of useful insects into crop fielddi6."1
threatened by herbivores by preventive induction of volatile
synomones and/or resistance genes.["' and the enhanced production of valuable flavor compounds. Preliminary induction
experiments with J A in cell suspension cultures of N . tirhucun?
and P. lzmatus demonstrated, however, that emission of volatiles
remains restricted to only a few compounds and does not show
the full pattern of compounds from the JA- or coronatin-treated
differentiated. intact plant.
-
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Experimentul Procedure
Freshly detached plantlets (with 2-5 leaves) of the plants listed in Table 1 were
placed in solutions of racemic rran.r-JA (10&molmL-') or coronatin (50 and
100 nmolml") in tap water. Following 10 h of preincuhation. the plants were
placed in a closed system (ca. 750 mL), and the volatiles were collected on a small
charcoal trap (1.5 mg) by air circulation [21] over 20 h. After desorption of the
volatiles from the charcoal with dichlorornethane (30 pL), the compounds were
analyzed by GC-MS (DB1 silica gel capillary column, 10 m x 0.31 mm: temperature
program: 50'C (2 min), thenanincreaseof 10-Cmin-l to 200"C;detection: Fisons
M D 800 mass spectrometer, G C interface at 260 C. scan range: 35-300 D a s - ' .
The mixture of compounds released from freshly detached plantlets placed i n water
served as a control. Plants: P. lunarus and Z. n7uy.r were cultivated as described i n
ref. [18]. Cerhuroiamrw,iii, cv. Sirtrrki was kindly provided by Prof. Dr. M. Dicke,
Agricultural University. Wdgeningen, The Netherlands. All other plants were from
the Botanical Garden of the University of Bonn.
Received: December 22, 1994
Revised version. March 6, 1995 [Z7570IE]
German version: Anxew. Cliem. 1995, 107, 1715- 1717
Keywords: induced volatiles . jasmonic acid . phytohormones
G. Semhdner, B. Parthier, Annu. Rev. Plunt Physiol. Plunr. M u / . B i d . 1993,44,
569.
B. A. Vick, D. C Zimmermann, Plan1 Physiol. 1984, 75, 458
R. A. Weidhase. H. Kramell, J. Lehmann, H. Liehisch, W, Lerhs, B. Parthier.
PIanr Sri. (Limerick, lrel.) 1987. 5f. 177.
I. Ueda. J. Kato, Plum Physiol. 1980. 66, 246.
M. Saniewski, J. Czapski, Esperientia 1985, 41. 256.
1. Nuske, F. Bublitz, J Busir Microhiol. 1993, 33, 241.
K . Tamura, Y. Takikawd, S. Tsuyumu, M. Goto, M. Watanahe, Nipj~on
Shokuhiirrir Byori Gukkaiho 1992, 58, 276.
F. Greulich. T. YOShlhdrd, H. Toshima, A. Ichihara. Ahstrurr of the X V lnr.
&JtUnicU/ C o n g r m , Tokio, 1 9 3 . p. 41 52.
Y. Koda, Y OkdZdWa. Plant re[/ PhJ'.SlO[.1988, 29, 969.
E. Falkenstein, B. Groth, A. Mithafer, E. W. Weiler, Plunro 1991, INS.
Pericyclic Reactions in Nature:
Spontaneous Cope Rearrangement Inactivates
Algae Pheromones**
Wilhelm Boland," Georg Pohnert, and Ingo Maier
Dedicuted to Professor Huns-Jurgen Bestmunn
on the occasion qf'his 70th birthday
Female gametes of marine brown algae use olefinic C, hydrocarbons as chemical signals to trigger the release of and/or
attract conspecific flagellated motile male sex cells.[', 21 In 1971
Muller et aLL3'isolated ectocarpene (2a), the pheromone of the
cosmopolitan brown algae Ectocurpus siliculosus. It soon
proved to be the prototype of a whole series of structurally
related 6-substituted cyclohepta-l,4-dienes, which attract male
gametes or induce their mass release (release factors). The most
frequently occurring compounds include dictyotene ( l),I4I desmarestene (3),[51
and lamoxirene (4) .['* 'I The latter is typical for
the highly evolved order Laminariales, in which the pheromone
induces spermatozoid release prior to attraction. The threshold
concentration of male response towards the signal is typically
found in the range of 10 nmolL-' to 0.01 nmolL- ', depending
upon algae species and pheromone function
c
r
1
316.
H. Gundlach. M. J. Muller, T. M. Kutchan, M. H. Zenk, Proc Nut/. Acad S i .
U S A 1992-89. 2389.
E. W. Weiler, T. M. Kutchan, T. Gorba. W. Brodschelm, U. Niesel. F. Bublitr.
FEES Lerr. 1994. 345. 9.
E. E. Farmer, C. A. Ryan, Proc. Narl. Acud. Sci. U S A 1990, 87, 7713.
E. E. Farmer, C. A. Ryan, Plunr Cell 1992, 4. 129.
H. J. Zeringue, Phytorhemi.strv 1992, 31. 2305.
M. Dicke. M. A. Sahelis, J. Takabayashi, J. Bruin, M . A. Posthumus, J Chiwn.
Erol. 1990, 16. 3091
T. C. J. Turlings, J. H Tumlinson. Proc. Narl. Acud. Sci. U S A 1992. 89.
8399.
J. Hopke, J. Donath, S. Blechert. W Boland. FEES Lrti. 1994, 352, 146.
H. Dittrich, T. M. Kutchan. M. H. Zenk, FEBS Lerr. 1992. 309, 11462.
J. P. MetrauX, H. Signer, J. Ryals, E. Ward, M. Wyss-Benr, J. Gaudin, K.
Raschdorf. E. Schmid, W. Blum, Science 1990 250. 1004.
W. Boland, P. Ney, L. Jaenicke, G. Gassmann in Anolrsis of Volutilcs (Ed.: P.
Schreier). Walter De Gruyter, Berlin, New York, 1984, p. 371
3
4
Recently we have shown that female gametes of marine
brown algae use C,, fatty acids as starting materials in the
biosynthesis of 1 and 2 a (Scheme 1).[8.91The precursor of dictyotene (1) was shown to be arachidonic acid, whereas ectocarpene (2a) was found to originate from cis-eicosa5,8,11,14,17-pentaenic acid (5). The first steps of fatty acid
activation remain unknown, but by analogy with the biogenesis
of 2 in higher plants,["] a 9-hydroperoxy fatty acid 6 (9HPEPE) is implicated as the first 0-functionalized intermediate.
A hydroperoxide lyase could cleave the reactive intermediate
9-HPEPE 6 directly to give the thermally labile cis-disubstituted
cyclopropane (1 R,2S)-7 a ( C , ,) and the C , dicarbonyl fragment
8 (Scheme 1). Divinylcyclopropanes of type 7 are thermally
labile and rearrange in a spontaneous [3,3] sigmatropic reaction
[*I Prof Dr. W. Boland. DipLChem. G. Pohnert
lnsritut fur Organische Chemie und Biochemie der Universitdt
Gerhard-Domagk-Strasse 1, D-53121 Bonn (Germany)
Telefax: Int. code (228)735388
Dr. I Maier
Fakultit fur Biologie der Universitlt Konstanz (Germany)
[**I Biosynthesis of Algae Pheromones, Part 4. This work was supported by the
Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.
We thank Prof. Dr. D. G. Muller (Universitlt Konstanz) for his support. Part
3: ref [17].
+
1602
0 VCH Ver/ugsgur/l.schufrm h H , 0-69451
Weinherm, 1995
057(1-~1833~Y5~15/5-1602
$ 10.00+ .25:0
Angeu. Cliem. lnt. Ed EngI. 1995, 34, No. li
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