I

Natural Acetylenic and Olefinic Compounds,

excluding Marine Natural Products
C.M.SCRIMGEOUR

1 Introduction
This report covers the same topics as does the corresponding chapter in the
first volume of this series. The bulk of it is concerned with polyacetylenic and
other acetylenic aliphatic natural products while the remainder deals with
olefinic compounds not obviously included in the other chapters. The litera-
ture coverage is for 1978-9 plus a few earlier reports not previously included.

2 Natural Acetylenic Compounds

Introduction. - This two-year spell has again been one of consolidation rather
than dramatic progress. A number of new compounds, mainly related t o
previously known structures, have been reported. A number of new sources
of known compounds have also been reported. Many of these reports concern
the physiological role or chemotaxonomic application of acetylenic com-
pounds. Four general reviews about polyacetylenes have appeared,’+ covering
the work of the past decade or more. While Bohlmann’s output has continued
to focus on terpenoid compounds, he still remains the most prolific con-
tributor t o this field.
New Polyacetylenic Compounds. - The majority of new compounds are found
in species within the family Compositae. A CISenediynene (1) and the related
dihydro-compound (2) were isolated from the roots of various South African
species of the genera Athanasia and Pentzia.’ These acids are of interest as
possible intermediates in the biosynthesis of polyacetylenes from crepenynic
acid. The linoleyl ester of (1) was also identified! In his continuing study of
South African members of the Compositae, Bohlmann identified a related
pair of C18 compounds ( 3 ) and (4) from a number of species of Seneciu.’ The

E. R. H. Jones and V. Thaller,Methodicum Chimicum, 1978,11, 175.

’ E. R. H. Jones and V. Thaller, in ‘The Chemistry of the Carbon-CarbonTriple Bond’,
ed. S. Patai, John Wiley, London, 1978, Ch. 14.
K. E. Schulte, East. Pham., 1979,22, 85.
K. E. Schulte, Korean J. Pharmacogn. (Saeng’yakhakJoeji), 1978,9, 11.
’ F. Bohlmann and C. Zdero, Phytochemistry, 1978,17, 1595.
F. Bohlmann and K.-H. Knoll, Phytochemistry, 1979, 18,995.
’ F. Bohlmann, C. Zdero, and A. A. Natu, Phytochernistry, 1978, 17, 1757.
2 Aliphatic and Related Natural Product Chemistry

two c18 compounds (1) and (2) have also been reported, occurring a s their
methyl esters in Athanasia tridens,' along with the new C17 olefin derivative
(5). Bohlman has suggested that (5) is biosynthesized by loss of carbon
dioxide and water from the P-hydroxy c18 compound ( 6 ) . Clibadium cf.
glomeratum has also yielded a new C17 compound (7).' Further C1, com-
pounds are related to dehydrofalcarinone; (8) and ( 9 ) were identified in
various South African species of Nidorella,lowhile the South American Diotis
maritima yielded the dihydroderivative ( l o ) , related to (8)." One new C16
compound has been identified. The aldehyde (11) was found in Siegesbekia
jorullensis. l 2
A number of C13 and C14 compounds have also been reported from various
members of the Compositae. Bohlmann identified four new thiophen deriva-
tives (12)-(15) from Cullumia setosa,13 along with other known thiophens.
A polyacetylene has been isolated for the first time from Brickellia Ea~iniata.'~
This is a new C14compound, with a novel pattern of unsaturation (16), and it
occurs as a mixture of stereoisomers. The stereochemistry has not yet been
determined. A study of compounds that are capable of stimulating the
germination of safflower rust (Puccinia carthami) and which are produced by
germinating safflower (Carthamus tinctorius) revealed a number of poly-

F. Bohlmann and C. Zdero, Phytochemistry, 1979,18, 1736.

H. Czerson, F. Bohlrnann, T. F. Stuessy, and N. H. Fischer, Phytochemistry, 1979,18,
257.
lo F. Bohlmann and U. Fritz, Phytochemistry, 1978,17,1769.
J. de Pascual Teresa, A. F. Barrero, and A. San Feliciano, An. Fig Quim., Ser. B,
Quim., 1977,73, 1525.
F. Bohlmann, J . Jakupovic, C. Zdero, R. M. King, and H. Robinson, Phytochemistry,
1979,18,625.
l3 F. Bohlmann and K.-H. Knoll, Phyfochemistry, 1979,18,1060.
l4 F. Bohlinann, A. Suwita, and T. J . Mabry, Phytochemistry, 1978,17, 763.
Natural Acetylenic and Olefinic Compounds 3

OAc
-
- -
-
OH
(8)

OH
(12) R = H
(13) R = Me

(14) R = H
(15) R = Me
4
---- Aliphatic and Related Natural Product Chemistry
- -

--- - -

(19)
/

acetylenic hydrocarbon^.'^ A number of these are C13 compounds that are

new to this well-studied species, and (17)-( 19) are new compounds. A careful
re-examination of t h e polar fraction of the aerial parts of Centaurea ruthenica
revealed over twenty new compound^.^^ Most of these are C13 compounds,
along with some Czo and C14 compounds, all of them present in trace
amounts. Complete separation of the components was not always possible,
but the structures (20)-(48) were unravelled from spectroscopic evidence.
'The new compounds help t o extend the biosynthetic schemes for these
compounds.
OH
= -

(21) R = H
(22) R = OH

OH

15 R. G. Binder, R . E. Lundin, S. Kint, J . M. Klisiewicz, and A. C. Waiss, Jr., Phyto-

chemistry, 1978,17, 315.
l6 R. Jente, F. Bohlmann, and S. Schoneweiss, Phytochemistry, 1979, 18, 829.
Natural Acetylenic and Olefinic Compounds 5

\
6 Aliphatic and Related Natural Product Chemistry
R2

(35) R' = Ac, Rz= OH

(36) R' = H, R2= OMe

(37) R' = Ac, R2= OH

(38) R' = H, Rz= OMe

R2
-
I _
-
- -
- 0R'

(39) R' = Ac, R2= OH

(40) R' = H, R2 = OAc

(42) R ' = H , R2= OAc Ri

- - - OH
- - -
OH
(45)

% HO
Natural Acetylenic and Olefinic Compounds 7

-
- -
- -
- -
- OAc

(47)

Bohlmann has also discovered a number of C I 2 compounds among

members of the family Compositae. The sulphur-containing compound (49)
occurs in Chrysanthemum coronarium, along with a number of known,
related cornpound~.'~ErniZiacoccinea and E. sagittata afforded a number of
C12 compounds (50)-( 54),which are suggested as the biosynthetic precursors
of the better known CI1 compounds.'* Two representatives (55) and ( 5 6 ) of
a new type of chloro-aromatic thiophen compound occur in Helichrysum
tenuifolium and H, pandumturn, along with the related, non-aromatized
compound (57).19 A chloro-enol ether (58) has been proposed as the bio-
synthetic precursor of these compounds, as shown in Scheme 1.

(50) R = Me
(51) R = H

- - OH
- -
OH OH
(52) R = Me
(53) R = H (54)

F. Bohlmann and U. Fritz,PhytochePnistry, 1979,18, 1888.

l8 F. Bohlmann and K.-H. Knoll,Phytochemistry, 1978, 17,557.
l9 F. Bohlmann and W.-R.Abraham, Phytuchemistry, 1 9 7 9 , 1 8 , 839.
8 Aliphatic and Related Natural Product Chemistry

= J Q - 0

a c1
(55) (56)

OH OMe

Q - G C l

(57)

hr rv rv hr hr hr hr N

Scheme 1
Natural Acetylenic and Olefinic Compounds 9

A number of Cll acetylenes (59)-(67) occur in Cineraria species,20and the

chemotaxonomy of the genus Cineraria is discussed by Bohlmann with refer-
ence to these and related compounds. Several sources of new Clo compounds
have been found. These compounds are derivatives of matricaria ester, with
which they often co-occur. The lactme ( 6 8 ) was isolated from Solidago
altissima,21 and the seasonal variation of its concentration and those of
matricaria ester and dehydromatricaria ester was observed. Chrysotharnnus
parryi gave four new derivatives of matricaria ester, i.e. (69)-(75).22A number
o f known compounds were isolated from Artemisia absinthium, along with a
new thiophen derivative of dehydromatricaria ester ( 76).23Two C l o furano-
acetylenes ( 7 7 ) and ( 7 8 ) were identified in Felicia f i l i f ~ l i a . ~ ~

(72) R = OAc
(73)R=OH
(70) R = 0

2o F. Bohlmann and W.-R. Abraham, Phytochemistvy, 1978, 17, 1629.

21
K.-I. Ichihara, T. Kawai, and M. Noda, Agric. Biol. Chem., 1978, 42, 427.
22 F. Bohlmann, C . Zdero, H . Robinson, and R . M. King, Phytochemistry, 1979, 18,
1519.
23 H. Greger, Phytochemistry, 1978, 17,806.
24 F. Bohlmann and U. Fritz, Phytochemistvy, 1979, 18, 1221.
10 Aliphatic and Related Natural Product Chemistry

(77)

A number of compounds were isolated from the roots of Pituranthus

tortuosus (Umbelliferae),25 and three of these are new compounds. The
structures of ( 7 9 ) and (80) were determined by spectroscopic and chemical-
modification methods. A third compound was not fully characterized, but
was shown t o contain the part structure (81).

I II
OH 0
(79)

RZ
-
- -
- R'

(81)
The fungus Peniophora resinosa yielded the new compound (82) in its
(+)-form, along with related known compounds.26 Cultures of the fungus
P o l y p o m s anthracophilus produced a number of C polyacetylenes, among
which one new isomer (8 3) was d e t e ~ t e d . ~
An' interesting collection of long-
chain polyacetylenic and acetylenic compounds has been reported from a
sponge of the genus SiphonchaZina.28 These compounds, (84)-(89), are
HO
OH
-
- -
- -
-

(82) 1-J (83)

OMe

" K . E. Schulte and B. Potter, Arch, Phann. (Weinheim, Ger.), 1977, 310, 945.
26 M. Ahmed, J . W. Keeping, T. A. Macrides, and V. Thaller, J. Chem. Soc., Perkin
Trans. I , 1978, 1487.
D. G. Davies, P. Hodge, P. Yates, and M. J. Wright, J. Chem. SOC., Perkin Trans. 1,
1978,1602.
l8 M. Rotem and Y. Kashman, Tetrahedron L e t t . , 1979, 3193.
Natural Acetylenic and Olefinic Compounds 11
marine natural products, but sufficiently similar t o some non-marine com-
pounds to be mentioned here. Unlike the compounds found in Reniera fulva,
( 8 8 ) and ( 8 9 ) only contain terminal hydroxyl groups, leaving unresolved the
problem of chirality raised in the previous review.

(85) m + n = 12 (m,n 2 1)
(86) m = 5, n = 3

(87)m + n = 10 (mor n = 1)

Other Acetylenic Compounds. - Six long-chain monoacetylenic compounds

(90)-(95)have been found in the Amazonian Laurel, Licaria r n a h ~ b aThe
.~~
stereochemistry of the y-lactone was determined by spectroscopic (mainly
'H n.m.r.) methods and from information about the circular dichroism of

HL-t
H*C
(90) R' = H, R2= (CHJ,,C=CH; CY-OH (92)
H
o*
Me
R' = H, R2= (CHJ13CsCH, CY-OH
(91) R' = (C&),,C=CH, Rz= H; &-OH (93) R' = (CHJ,,C=CH, R2= H; &-OH
(94) R' = H, R2= (CHJ,,C=CH; @-OH
(95) R' = (CH,),,C=CH, R2= H; P-OH
29
J . C. Martinez, M. Yoshida, and 0. R . Gottlieb, Tetrahedron Lett., 1979, 1021.
12 Aliphatic and Related Natural Product Chemistry
these and related compounds. Compounds ( 9 0 ) and (91) are unstable, and
had to be studied within a few days of isolation. These compounds co-occur
with the related olefinic and saturated compounds. A further acetylenic
isocoumarin, 8-hydroxycapillarin ( 9 6 ) , has been isolated from Artemisia
dra~unculus.~~

Known Polyacetylenic Compounds. - Known compounds often co-occur

with the new compounds described above, and these are not further discussed.
There are, however, a number of reports of known compounds from new
plant sources. Many of these reports stem from chemotaxonomic studies of
the complex genera of the Compositae. Table 13’-62 lists the plant sources
studied, along with the main types of acetylenic compounds found therein,
but excludes sources mentioned in the foregoing and following sections.

30 H. Greger and F. Bohlmann, Phytochemistry, 1979,18, 1244.

31 F. Bohlmann, C. Zdero, R. M. King, and H. Robinson, Phytochemistry, 1979, 18,
1894.
32 H. Greger, Phytochemistry, 1979,18, 1319.
3 3 H. Greger and F. Bohlmann, Phytochernistry, 1979,18, 1244.
34 H. Greger, PlantaMed., 1979, 35, 84.
3 5 F. Bohlmann, W. Knauf, R. M. King, and H. Robinson, Phytochemistry, 1979, 18,

101 1
36 F. Bohlmann, N. L. Van, T. V. C. Pham, J. Jakupovic, A. Schuster, V. Zabel, and
W. H. Watson, Phytochemistry, 1979,18,1831.
37 F. Bohlmann and J. Jakupovic, Phytochemistry, 1979,18, 119.
” F. Bohlmann, L. Dutta, H. Robinson, and R. M. King, Phytochernistry, 1979, 18,
1889.
39 F. Bohlmann and C. Zdero, Phytochemistry, 1979,18, 95.
40 F. Bohlmann and J. Jakupovic,Phytochemistry,1979,18,1367.

4 1 F. Bohlmann and C. Zdero, Phytochemistry, 1979,18, 336.

4 2 F. Bohlmann and W;R. Abraham, Phytochemistry, 1979,18,668.
4 3 F. Bohlmann, M. Lonitz, and K.-H. Knoll, Phytochemistry, 1978, 17, 330.
44 F. Bohlmann, U. Fritz, H. Robinson, and R. M. King, Phytochernistry, 1979, 18,

1749.
4 5 F. Bohlmann and L. N. Dutta, Phytochemistry, 1979, 18,676.
46 F. Bohlmann, P. K. Mahanta, and C. Zdero, Phytochemistry, 1978, 17, 1935.

47 F. Bohlmann and U. Fritz, Phytochemistry, 1979,18, 1080.

4 8 F. Bohlmann, C. Zdero, H. Robinson, and R. M. King, Phytochemistry, 1979, 18,

1675.
4 9 F. Bohlmann and C. Zdero, Phytochemistry, 1979,18,1185.
F. Bohlmann, P. K. Mahanta, J. Jakupovic, R. C. Rastogi, and A. A. Natu, Phyto-
chemistry, 1978,17,1165.
5 1 F. Bohlmann and C. Zdero, Phytochernistry, 1978,17, 2032.

5 2 F. Bohlmann and A. Suwita, Phytochemistry, 1978,17, 1929.

53 F. Bohlmann and M. Grenz, Phytochernistry, 1979,18, 3 3 4 .

Natural Acetylenic and Olefinic Compounds 13
Table 1 New sources of known acetylenic compounds within the family
Comp ositae

Species New compound types Reference

Acourtia thurberi c13 31
Artemisia dracunculus 32,33
Artemisia spp. I C, 7, dehydrofalcarinone
34
35
Baccharis spp. ClO, Cl,
Berkheya spp. thiophens 36
Calea urticifolia ‘17 37
Chrysothamnus nauseusus ClO 38
Cnicothamnus lorentzii c
1 3 39
Conyza spp. ClO 40
Cotula hispida Go, c17 41
Doronicum pardalianches c
1 3
42
Flaveria chloraefolia thiophens 43
Gochnatia rusbyana c13 39
Haplopappu s venetu s ClO
44
Helianthus lehmannii deh ydro falcarin-one/-ol 45
Helichrymm spp. C , 3, chloroenol ether 46
Hereromrna simplicif o lium , c17
47
H. decurrens
Heterotheca grandiflora ClO 48
Heterotheca spp. c17, c14, c10 49
Inula spp. c13 50
Lasthenia spp. C14,C,,, thiophen, disulphide 51
Leontonyx spp. C, 3, thiophen 52
Microglossa rnespilifolia ‘17
47
Munnozia spp. C13,thiophen 53
Onoseris gnaphaloides c13 39
Ophryosponis angustifolius ‘13 54
Peu cedanum ore0 selinum falcarindiol 55
Pluchea foetida thiophen 56
Polyanthim nemorosa c13 54
Senecio spp. c17, ‘13 57
Tagetes microglossa t hio phen 58
Tagetes spp. C13,thiophen 59
Tarchonanthus trilobus C13,thiophen 60
Vernonia saltensis thiophen 61
Vernonia spp. thiophen 62

54 F. Bohlmann and C. Zdero, Phytochemistry, 1979,18,145.

55 E. Lemmich and C. Zdero, Phytochemistry, 1979,18,1195.
56 F. Bohlmann and P. K. Mahanta, Phytochernistry, 1978, 17, 1189.
5 7 F. Bohlmann, C. Zdero, D. Berger, A. Suwita, P. Mahanta, and C. Jeffrey, Phyto-

chemistry, 1979, 18, 79.

5 8 V. A. Castro and 0.C. Castro, Rev. Latinoam. Quim., 1978,9, 204.

5 9 F. Bohlmann and C. Zdero, Pkytochemistry, 1979,18, 341.

F. Bohlmann and A. Suwita, Phytochemistry, 1979,18,668.

6 1 F. Bohlmann, P. K. Mahanta, and L. N. Dutta, Phytochemistry, 1979,18, 289.

6 2 F. Bohlmann, G. Brindopke, and R. C. Rastogi, Phytochemistry, 1978, 17,475.

14 Aliphatic and Related Natural Product Chemistry
Structure Determination. - The structures of the majority of the new and
known compounds were deduced by the conventional spectroscopic methods,
coupled (on occasions) with chemical transformations. High-field (2 70 MHz)
proton magnetic resonance spectroscopic studies and the use of lanthanide
shift reagents are becoming routine, and allow considerable information to be
obtained from mixtures which cannot be separated. Bohlmann has reported
the 13C n.m.r. spectra of two synthetic compounds.63 These compounds were
13C-labelled, and this allowed the assignment of the acetylenic carbons (see
Table 2). The potential of this highly structure-sensitive method is, however,
still limited by the larger samples required compared with 'H n.m.r.

Table 2 Carbon-13 n.m.r. shifts (p.p.m.)f o r two groups of labelled

compounds

Positw n Chemical sh iftlp.p. m.

of label
-
- -
- -
- -
- (1) (1) (11)
c-1 30.3 30.3
1 2 3 5 7
c-2 28.8 28.3

Cb 61.9 62.0
c-7 - 61.8

Synthesis. - The syntheses of two Clo alcohols from Polyporus anthraco-

, ~a~ Clo methyl ether found in both Lentinus lepideus and Leuco-
p h i l ~ s of
paxiZZus giganteus,26 and of (*)-helenyolic acid@ all used conventional
Chod kiewicz coupling.
A useful route t o pure (2) and ( E )Cg, C 6 , and C7 alk-3-en-1-ynes has been
reported.65 The mixture of isomers prepared by the usual synthetic routes is
separated by spinning-band distillation of the trimethylsilyl derivatives. These
derivatives, formed from the alkyne, n-butyl-lithium, and trimethylsilyl
chloride, increase both the stability of the terminal alkyne and the difference
in boiling point of the two isomers. The parent hydrocarbon is regenerated by
treatment with silver nitrate or potassium fluoride.
Bohlmann confirmed the structure of three furano-polyacetylenes from
Alphonsea ventricosa by synthesis.a The route is a general one to a-
substituted furans, and involves the reaction of a nitrile with allylmagnesium
chloride and treatment of the resultant keto-olefin with osmium tetroxide
and sodium hydrogen sulphite. Alternatively, treatment of the osmate ester
with base gives the diol (Scheme 2).
" F. Bohlmann and M. Brehm, Chem. Bev., 1979,112,1071.
64 T.B. Patrick and G. F. Melm, J. 0%.Chem., 1979,44,645.
6 5 I. W. Farrell, M. T. W. Hearn, and V. Thaller, J. Chem. Soc., Perkin Trans I , 1978,

1485.
66 F. Bohlmann, F. Stohr, and J . Staffeldt, Chem. Ber., 1978,111, 3146.
Natural Acetylenic and Olefinic Compounds 15

OH

"Ki""
0
I
R /Q
Reagents: i , w MgCl; ii, OsO,; iii, OH-; iv, NaHSO,
Scheme 2

A modified synthesis of 1,4-enynes6' (Scheme 3 ) and a stereospecific

synthesis of terminal (E)-enynes68 (Scheme 4) have possible applications in
the synthesis of polyacetylenic natural products.

R'

(R' = alkyl; R2= alkyl or aryl)

Scheme 3

I
-0
Scheme 4

Biosynthesis. -Many of the new compounds described above have been

proposed as further intermediates in the generally accepted schemes of bio-
synthesis, and some reports include postulated biosynthetic routes to novel
compounds. However, there have only been two reports of labelling studies
during the past two years.
The biosynthesis of wyerone ( 9 7 ) by the broad bean (Vicia faba) has been
clarified by a study using material infected with Botrytis ~inerea.~'Wyerone
is only produced in response to infection, and previous work, using healthy

61 V. Calo, L. Lopez, G. Marchese, and G . Pesce, Tetrahedron Lett., 1979, 3873.

68 L. Crombie, N. A. Kerton, and G. Pattenden, J. Chem. Soc., Perkin Trans 1 , 1979,
2136.
69 R. 0. Cain and A. E, A, Porter, Phytochemistry, 1979,18, 322.
16 Aliphatic and Related Natural Product Chemistry

(97)
tissue, produced understandabl inconclusive results. This new study showed
K!
significant incorporation of [ 1- Clacetate, [ 2-14C]malonate, and [n,9,10-%1-
oleate into wyerone, increasing in that order. This strongly suggests that
wyerone is derived from oleate, presumably via crepenynate, but leaves the
problem of the subsequent double-bond rearrangement unresolved
The role of matricaria esters as intermediates in the biosynthesis of several
metabolites of Polyporus anthracophilus has been established by tracer
studies.27 When a mixture of (E,E)-[1-l4C1- and (2E,82)-[ 1-14C]-matricaria
esters, ( 9 8 ) and ( 9 9 ) ,was fed to a culture of the fungus, specific incorporation
into (E,E)- and (2,Z)-matricariol, (100) and (101), and the dimethyl ester
(102) was observed. These results show that the fungus has the ability t o
reduce the ester function to an alcohol and also to isomerize an ( E ) 2,3
double-bond to the (2) configuration. The production of (102) shows the
further ability to oxidize the terminal methyl group, presumably with the
hydroxy-matricaria esters (103) and (104) as intermediates.

(99)

Ho-[as (102)]

(103) HO (104)
Natural A‘cetylenic and Olefinic Compounds 17
Chemotaxonomy and Physiological Properties. - Many of the reports listed
in Table 1 include applications of the distribution of polyacetylenic com-
pounds to the complex problem of the taxonomy of members of the
Compositae. This topic has been reviewed at some length,70 and one report on
the systematics of the genus A n a c y c Z ~ sincludes
~~ a discussion of the existing
data on polyacetylene distribution.
The role of polyacetylenes as phytoalexins (plant defence substances) has
received some attention. The role of polyacetylenes in resistance t o fungal
infections of safflower and broad bean has been reviewed.72 A study of
germinating lentils (Lens culinaris) that were infected with Botrytis ~ i n e r e a ~ ~
has shown that wyerone (97) and the related epoxide and dihydro-compound
are produced as phytoalexins. This suggests that the genus Lens is more
closely related to Vicia than it is t o Pisum or Lathyrus, which d o not produce
furano-acetylenes. Both falcarindiol (105) and falcarinol (106), isolated from
the roots of ground elder (Aegopodium podagraria), were found to inhibit
the germination of fungal spores, but the diol was much more effective in
-
- -
- I =-
OH R
(105) R = OH
(106)R = H
this respect.74 Dehydromatricaria ester and lactone have been shown to
inhibit the germination of millet seeds.21There has been a further account of
the nematocidal properties of C13 trienetriynes from Carthamus t i n c t o r i u ~ . ~ ~
The action of polyacetylenes as insecticides, nematocides, and antibiotics and
their action against vertebrates has been reviewed.76 This review includes a
report of the phototoxicity of some thiophen compounds, and this topic is
described further in a report of the photosensitizing behaviour of a-terthienyl
and 5-(but-3-en-l-ynyl)-2,2’-bithienyl,isolated from Tagetes species. 77

3 Natural Olefinic Compounds

Introduction. - This part of the review describes those long-chain olefinic
compounds which do not obviously fall within any other class of compounds.
A few of these compounds are related t o acetylenic natural products, both in
source and probable biosynthesis, while the remainder have only an aliphatic
chain of some length in common.
70 6 The Biology and Chemistry of the Compositae’, ed. V. H. Heywood, J. B. Harborne,

and B. L. Turner, Academic Press, London, 1979,Vols. I and 11.

71
H. Greger, Biochem. Syst. Ecol., 1978,6 , 11.
H. Grisebach and J. Ebel, Angew. Chem., Int. Ed. Engl., 1978,17,635.
73 D. J. Robeson, Phytochemistry, 1978,17,807.
74
M. S . Kemp, Phytochemistry, 1978,17,1002.
7 5 K. Munakata, ‘Advances in Pesticide Science’, ed. H. Geissbuhler, Pergamon Press,

Oxford, Part 2,p. 295.

76 G. H. N. Towers and C.-K. Wat, Rev. Latinoam. Quim., 1978,9,162.

77 G. F. Q. Chan, M. M. Lee, J. Glushka, and G. H. N. Towers, Phytochemistry, 1979,

18,1566.
18 Aliphatic and Related Natural Product Chemistry
Olefms Related t o Acetylenes. - A new tetrahydrofuran derivative (107)
from Helichrysum aureo-nitens= is likely to be related t o the acetylenic
compounds found in other species of that genus. The structure was deter-
mined by high-field 'H n.m.r. (270 MHz) of both (107) and its acetate, in
conjunction with solvent shift effects. The known CI5 hydrocarbon (108) has
now been found in Ligularia macrophylZa.m Olefinic compounds from Licaria
mahuba were mentioned when describing the acetylenic compounds from
that specie^.^'

Other Olefinic Compounds. - Two novel 0-triketones (109) and (110) have
been isolated from the larval mandibular glands of Anagasta kuehniella and
other lepidoptera," and this is the first report of such compounds from
insects. The compounds, which are optically active, were examined by
spectroscopic techniques. The 'H n.m.r. data suggest that both compounds
are fully enolized in deuteriochloroform solution. The antibiotic and
behavioural effects of (109) and (110) are being studied.

R
(109) R = OH
(1 10) R = H

The stereochemistry of the antibiotic thermozymocidin has been revised

t o the all-2 form" rather than the previously suggested a l l 3 form. The chiral
lactone (111) was prepared by a stereospecific synthesis and shown to be
identical with that obtained from the open-chain natural product. Three
aliphatic alkaloids, (112)-( 114), that have C12 chains have been identified

(1 12) R' = R*= Me

(113) R' = Me, R2=H
(114) R' = R2= H
78 F. Bohlmann and J. Ziesche, Phytochemistry, 1979, 18,664.
79 F. B o h h a n n and M. Grenz, Phytochemistry, 1 9 7 9 , 1 8 , 4 9 1 .
8o A. Mudd, J. Chem. SOC.,Chem., Commun., 1978,1075.
81 C . H. Kuo and N. L. Wendler, Tetrahedron Lett., 1978, 211.
Natural Acetylenic and Olefinic Compounds 19
from spectroscopic data in extracts of Dicarpellum pronyensis.82 The
insecticidal properties of the known isobutylamide ( 1 15) from Piper
n i g r ~ r have
n ~ ~ been studied.
A new metabolite of sorbic acid ( 1 16) has been found in cultures of the
fungus Mucor sp. A-7 3 .% The structure was determined spectroscopically, in
conjunction with periodate cleavage. The absolute configuration ( 2 S ,3R) was
established by stereospecific synthesis of the corresponding saturated com-
pound. Two new short-chain compounds (117) and (118) occur as aroma
constituents of the purple passionfruit (Passiflora e d u l i ~ ) . ~Both
' structures
were confirmed by synthesis.

OH OH

82 B. Adeoti, T. Sevenet, and M. Pais, Phytochemistry, 1978,17, 831.

a3 M. Miyakado, I. Nakayama, H. Yoshioka, and N. Nakatani, Agric. Biol. Chem., 1979,
43,1609.
a4 J. Kawabata, S. Tahara, and J. Mkutani, Agric. Biol. Chem., 1978,42,89.
a5 M. Winter, F. Naf, A. Furrer, W. Pickenhagen, W. Giersch, A. Meister, B. Willhalm,
W. Thommen, and G. Ohloff, Helv. Chim. A c t a , 1979,62,1 3 5 .