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Aliphatic and Related Natural
Product Chemistry
Volume 3


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A Specialist Periodical Report

Aliphatic and Related Natural
Product Chemistry
Volume 3

A Review of the Literature published
during 1980 and 1981

Senior Reporter

F. D. Gunstone Department of Chemistry,
University of St Andrews
Reporters
R. Baker University of Southampton

J. W. S. Bradshaw University ofSouthampton
W. W. Christie The Hannah Research Institute, Ayr
D. H. Grayson Trinity College, Dublin
R. H. Green Glaxo Group Research, Greenford, Middlesex
R. C. F. Jones University of Nottingham
P. F. Lambeth Glaxo Group Research, Greenford, Middlesex
R. F. Newton Glaxo Group Research, Ware, Hefts
S. M. Roberts Glaxo Group Research, Greenford, Middlesex
C. M. Scrimgeour University of Dundee

The Royal Society of Chemistry
Burlington House, London W I V OBN


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ISBN 0-8.5 186-662-X
ISSN 0142-7318

Copyright 0 1983
The Royal Society of Chemistry
All Rights Reserved
No part of this book may be reproduced or transmitted in any form
or by any means - graphic, electronic, including photocopying, recording,
taping, or information storage and retrieval systems - without
written permission from the Royal Society of Chemistry

Printed in Great Britain
by Whitstable Litho Ltd. Whitstable, Kent



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Foreword
This volume is the first in any of the series of Specialist Periodical
Reports to be produced from the authors' camera-ready typescripts.
We would choose that volumes such as this were typeset, because of
the compactness of such books relative to those prepared from
camera-ready copy, but, as indicated by the term Specialist, books
such as this can only ever serve a very limited readership. The
high costs of technical typesetting must therefore be shared amongst
a small number of books sold. At a time when many individuals and
librarians must critically scrutinise the list of bcoks that they
would wish to buy and then consider how much of that list they can
afford, the avoidance of the cost of typesetting will, we hope,
allow the information in these Reports to reach as wide an audience
as is practical.
Alongside the constraints placed on the budgets of many librarians,
many organisations have had to restrict or reduce the secretarial
help available to prospective authors. Several of the authors who
contributed to this volume have had to overcome such handicaps, even
to the extent of producing the typescripts themselves. Without
their co-operation, we would not have produced this volume.
The Royal Society of Chemistry

B 3 Starkeg

October 1982

(Editor, Booksj



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Contents

1

C h a p t e r 1 N a t u r a l A c e t y l e n i c and O l e f i n i c Compounds
B y C.M.Scrimgeour

1 Introduction 1
2 Natural Acetylenic Compounds

1

2.1 Introduction 1
2.2 New Polyacetylenic Compounds from
Terrestrial Plants

1

2.3 Known Polyacetylenic Compounds from
Terrestrial Plants

8


2.4 Acetylenic Compounds of Marine Origin

9

2.5 Biosynthesis of Acetylenic Compounds

12

2.6 Physiological Role of Polyacetylenic Compounds

3 Natural Olefinic Compounds
3.1 Isolation

3.2 Synthesis

References

17
18

23
26

Chapter 2 Acyclic Terpenoids
By D.H.Grayson

1 Introduction 26
2 Isoprene Chemistry 26
3 Irregular Systems 31
4 2,6-Dimethyloctane Group

4 . 1 Ocimenes

33

4 . 2 Myrcenes

34

4 . 3 Citronellyl Derivatives
4 . 4 Linalyl Derivatives

33

35

38

4 . 5 Geranyl and Neryl Derivatives

5
6
7
8

14

17

Sesquiterpenes
Diterpenes 59

Squalene 61
Polyterpenoids
References 6 2

54

61

42


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...

Aliphatic and Related Natural Product Chemistry

Vlll

C h a p t e r 3 I n s e c t Pheromones and R e l a t e d N a t u r a l P r o d u c t s

66

By R . Baker and J.W.S. Bradshaw

1 Introduction 66
2 Pheromones 66
2.1 Sex Pheromones of Lepidoptera 6 6
2.2 Aggregation Pheromones of Coleoptera 71
71


2.3 Sex Pheromones of Diptera

2.4 Pheromones of Hymenoptera - Bees, Wasps, and Ants

72

2.5 Other Pheromones 7 4

3 Defensive Secretions

74

4 Other Exocrine Products 78
5 Biosynthesis and Biotransformation 78
6 Separation and Structure-Elucidation Techniques
7 Synthetic Studies 81

80

7.1 Mono-unsaturated Derivatives 81
7.2 Di-unsaturated Derivatives 83
7.3 Tri-unsaturated Derivatives 87
7.4 Ketones, Alcohols, and Acetates

89

7.5 Epoxides 93
7.6 Lactones 93
7.7 Ketals


96

7.8 Spiroketals 98

References

101

Chapter 4 P r o s t a g l a n d i n s and Leukotrienes
By R.F. Newton, S.M.

1 Introduction 107
2 Synthesis of PGs A - F

108

2.1 Routes via the Corey Lactone

2.2 Glaxo Syntheses

107

Roberts, R.H. Green, and P.F. Lambeth

108

113

2.3 Conjugate Addition to 4-Substituted Cyclopentenones
2 . 4 Miscellaneous Procedures


121

3 Reactions of PGs A - F 123
4 Synthesis of Analogues of PGs A-F
4.1

Deoxyprostaglandins 126

4 . 2 Fluoroprostaglandins 133

4.3 Azaprostaglandins 135
4.4 Oxa- and Thia-prostaglandins 140
4.5 Miscellaneous Analogues

141

4.5.1 Cyclopentane-ring Variants
4.5.2 Lower Side-chain Variants

141

145

126

118


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ix

Contents

5 Synthesis of PGs G-I
6 Reactions of PGs G-I

147

149
7 Synthesis of Analogues of PGH
8 Synthesis of Analogues of PGI
8.1 Prostaglandin I l

152

8.2 6,9-Methano-PG12

153

8.3 6,9-Thia-PGI

8.4 Homo-PGI

151
152

157


158

8.5 Miscellaneous Analogues of PGI

158

161
Synthesis of Analogues of Thromboxane A2 1 6 2
PG Interconversions 170
Radiolabelled Prostaglandins 172
Stereochemistry of Prostaglandins, including Crystallographic and Spectroscopic Studies 172
Quantitation and Chromatography of Prostaglandins 1 7 3

9 Synthesis of Thromboxane B

10
11
12
13
14

14.1 Thin Layer Chromatography 174
14.2 High Pressure Liquid Chromatography 174
14.3 Gas-Liquid Chromatography of Prostaglandins

174

15 Biosynthesis, Metabolism, and Biological Activity of
Prostaglandins 176
16 Biosynthesis of Leukotrienes 178

17 Preparation o f 5-HPETE and 5-HETE 1 7 8
18 Preparation of Leukotriene A4 1 8 1
19 Preparation of LTC4, ll-trans-LTC4, LTD4, and LTE4 190
20 Preparation of LTB4 1 9 2
2 1 Leukotriene Analogues 196
22 Late Entries 197
23 Acknowledgements 1 9 8
References 199
Chapter 5 F a t t y A c i d s and G l y c e r i d e s

209

By F.D. Gunstone

1 Books and Reviews 209
2 Natural Compounds: Occurrence and Identification 209
2.1 Saturated and Unsaturated Acids
2.2 Oxygenated Acids

209

211

2.3 Cyclic and Branched-chain Acids

213

2.4 Vinylacetylenes and Other Compounds from Red Algae

3 Synthetic Compounds


215

3.1 General Procedures 215

214


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Aliphatic and Related Natural Product Chemistry

X

217

3.2 Synthetic Acids and Related Compounds
224

3.3 Glyceride Synthesis

224

4 Physical Properties
4.1 Gas Chromatography

224

225


4.2 High-performance Liquid Chromatography
226

4.3 N.m.r. Spectroscopy
4 . 4 Mass Spectrometry

226

4 . 5 Other Physical Properties

5 Chemical Reactions

226

227

5.1 Hydroperoxides and Peroxides - Formation and Reactions
5.1.1

Autoxidation

229

5.1.2 Photo-oxygenation

5.1.3 Other Chemical Hydroperoxidation Reactions
5 . 1 . 4 Enzymic Oxygenation
5.1.4.1 P l a n t systems
5.1.4.2


229

231

231

Animal systems 232

5.1.5 Procedures for Xeasuring Hydroperoxides
5.1.6 Antioxidants

234

5.2 Epoxides - Formation and Reactions

5.3 Hydrogenat ion

235

235
235

5.4 Other Double-bond Reactions

5 . 5 Reactions of the Carbonyl Group

6 Biological Reactions
de novo Synthesis

237


237
237

6.2 Chain Elongation and Desaturation
6 . 3 Xetabolism of Selected Acids

References

233

234

5 . 1 . 7 Secondary Oxidation Products

6.1

227

227

237

239

241

Chapter 6 L i p i d s

250


By W.W. C h r i s t i e

1 Introduction 250
2 Triacylglycerols and Related Lipids

250
3 Sterol Esters, Waxes, and Other Simple Lipids
4 Phosphoglycerides 2 5 3
4.1 Phosphatidylcholine and Analogues
4 . 2 Phosphatidic Acid

253

257

4.3 Phosphatidylserine
4 . 4 Phosphatidylinositol

257

258

4.5 Phosphatidylglycerol and Cardiolipin
4 . 6 Other Glycerophosphatides

259

258


252


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Contents

xi
4.7 Synthesis of Glycerophospholipids (general)

259

4.8 Phospholipids containing Spectroscopic Probes and

Other Sensitive Groups 262
4.9 Phospholipid Biosynthesis (general)
4 . 1 0 Phospholipids and Enzyme Function

263
263

5 Sphingomyelin and Other Phosphoceramides 2 6 4
6 Glycosyldiarylglycerols and Related Lipids 2 6 4
7 Glycosphingolipids 267
8 Other Lipids 2 6 9
9 Analytical Methods 2 7 2
10 Physical Chemistry 2 7 3
10.1 Theoretical Calculations

273


10.2 Infrared and Raman Spectroscopy 274
10.3 X-Ray and Electron Diffraction

275

10.4 NMR Spectroscopy 275

10.5 Differential Scanning Calorimetry 276
10.6 Other Physical Methods

11 Books and Reviews
References 2 7 9

277

278

C h a p t e r 7 Olefinic Microbial Metabolites, including
Macrocyclic Compounds
By R.C.F.

288

Jones

1 Non-macrocyclic Olefinic Microbial Metabolites
1.1

Pyran-Pyranoid Compounds


1.2 Butenolide Metabolites
1.2.1

Tetronic Acids

1.2.2

Miscellaneous 298

288

296

296

1.3 N-Heterocyclic Compounds

299

1 . 3 . 1 Pyrrolidines and Pyrroles

299

1.3.2

Piperidines and Pyridines 303

1.3.3


Other N-Heterocycles 305

1.4 Other Nitrogen-containing Metabolites

305

1.5 Miscellaneous Olefinic Microbial Metabolites

310

1.5.1 Cyclopentene Metabolites 312
1.5.2

Cyclohexene Metabolites 315

2 Macrocyclic Olefinic Microbial Metabolites 315
2.1 Polyoxo-Macrolides 317
2.1.1

Prelog-Djerassi Lactone 317

2.1.2

Neomethymycin 318

2.1.3

Mycinamycins 3 I8

288



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Aliphatic and Related Natural Product Chemistry

xii
2.1.4 Tylosin

320

2.1.5 Rosaramicin

322

2.1.6 Platenolides 322
2.1.7 Carbomycins and Leucomycins
2.2 Polyene Macrolides
2.2.1

Pentaenes

325

2.2.2 Heptaenes

326

325


2.3 Roridins and Verrucarins

326

2.4 Vermiculine and Pyrenophorin
2.5 Brefeldins

322

327

330

2.6 Milbemycins and Avennectins

331

2.7 Boromycin and Aplasmomycin

332

2.8 Orsellinic Acid Macrolides

336

2.9 RecifeiOli.de

337

2.10 Miscellaneous Macrocyclic Lactones

2.11 Cytochalasans and Chaetosoglobins
2.12 Ansamycins

344

2.12.1 Rifamycins
2.12.2 Actamycin

344
351

2.12.3 Streptovaricins

2.12.5 Macbecins

351

351

2.12.4 Herbimycins

351

2.12.6 Ansamitocins
2.12.7 Rubradirins

352
354

2 . 1 3 Other Macrocyclic Metabolites


References

357

354

338
342


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Natural Acetylenic and Olefinic Compounds
BY C. M. SCRIMGEOUR

1 Introduction
T h i s r e p o r t c o v e r s t h e same t o p i c s a s t h e c o r r e s p o n d i n g c h a p t e r
i n t h e p r e v i o u s volume, b u t i n a d d i t i o n i n c l u d e s a c e t y l e n i c and
o l e f i n i c compounds of marine o r i g i n .

A c e t y l e n i c compounds form t h e

b u l k of t h e m a t e r i a l , t h e o l e f i n i c compounds b e i n g t h o s e which a r e
n o t covered by o t h e r c h a p t e r s .

The l i t e r a t u r e covered i s t h a t f o r

1980-1.
2 N a t u r a l A c e t y l e n i c Compounds

2 . 1 1ntroduction.-

The r e s u l t s r e p o r t e d d u r i n g t h i s two-year s p e l l

A number of new compounds
continue t h e p a t t e r n previously noted.
a r e d e s c r i b e d and known compounds a r e r e c o r d e d from new s o u r c e s .

Two t o o l s a r e i n c r e a s i n g l y used
chromatography ( h . p . 1 . c . )

-

h i g h performance l i q u i d

and h i g h f i e l d ( 2 2 7 0 MHz) n u c l e a r

magnetic resonance ( n . m . r . )

spectroscopy.

Very l i t t l e new

s y n t h e t i c methodology h a s been r e p o r t e d .

2 . 2 N e w P o l y a c e t y l e n i c Compounds from T e r r e s t r i a l P l a n t s . - The
m a j o r i t y of new compounds have been i s o l a t e d from members o f t h e
l a r g e Compositae f a m i l y , and many a r e r e p o r t e d a s a r e s u l t of
Bohlmann's c o n t i n u i n g s t u d y of t h i s f a m i l y . Most a r e c l o s e l y
r e l a t e d to known s t r u c t u r a l t y p e s and t h e i r s t r u c t u r e s t h e r e f o r e

f o l l o w e a s i l y from s p e c t r a l d a t a .
r e s o l u t i o n n.m.r.

The growing use of h i g h

f o r t h i s purpose i s a p p a r e n t .

Unless o t h e r w i s e

i n d i c a t e d t h e s p e c i e s mentioned b e l o n g t o t h e Compositae.
Two CI7 hydrocarbons (1) and ( 2 ) w e r e i s o l a t e d from
1
Three s o u r c e s have r e v e a l e d oxygenated C1,

Leucanthemurn adustum

.

compounds of c l o s e l y r e l a t e d s t r u c t u r e .

The e p o x i d e s ( 3 ) and ( 4 )

were i s o l a t e d from Cacosrnia r u g o s a 2 and Cirsiurn japonicurn

3

r e s p e c t i v e l y , w h i l e t h e m i x t u r e of d i a c e t a t e s ( 5 ) and ( 6 ) w a s found

i n two P t i Z o s t e r n o n s p e c i e s 4


.


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Aliphatic and Related Natural Product Chemistrj

2

/ V V \ -

f

I

%

r

1

c

-

1

( 6 ) R1

A


number of new C17

been r e p o r t e d .

=

R2 =

6

.

R3

=

H

compounds r e l a t e d t o f a l c a r i n o l have a l s o

The a c e t a t e ( 7 ) o c c u r s i n V i g u i e r a incana a l o n g w i t h

.

d e h y d r o f a l ~ a r i n o l ~ Panar g i n s e n g
epoxide ( 8 )

Ac,


(Araliaceae) contains t h e

T h i s compound c o u l d a l s o b e o b t a i n e d f r o m f a l c a r i n o l

by e p o x i d a t i o n and t h e s t r u c t u r e was f u r t h e r confirmed by synthesis.
P.

g i n s e n g also c o n t a i n s t h e d i o l ( 9 ) 7 , and mass s p e c t r a l d a t a a r e

r e p o r t e d f o r b o t h ( 9 ) and t h e s a t u r a t e d d i o l o b t a i n e d by
hydrogenation.

The a b s o l u t e c o n f i g u r a t i o n of f a l c a r i n d i o l (10) i s

3 R , 8 S , which w a s shown by e x a m i n a t i o n o f t h e d i o l and mono-ol
8
m i x t u r e o b t a i n e d by h y d r o g e n a t i o n
A C15 a c e t a t e (11) w i t h a

.


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Natural Acetylenic and Ofefinic Compounds

3

structure related to falcarinol has been isolated from H e Zi a n t h u s
angustifoZius 9


.

Two C16 amides (12) and (13) occur in A c h i l l e a t o m e n t o s a
along with a number of related olefinic amides.

10

.

11
The C14 angelate ester (14) occurs in S e n e c i o c Z e v e l a n d i i
Interestingly, the isolation of this compound is reported along
with that of the first known acetylenic monoterpene (15) and the
related olefin (16). It is suggested that the co-occurrence of
( 1 4 ) , (15) and (16) may support the assumption that the acetylenic
bond is formed by dehydrogenation of a cis double bond.
L y c o p e r s i c o n escuZentum (Solanaceae) produces ( 1 7 ) along with
falcarindiol and falcarinol after inoculation with C l a d o s p o r i u r n


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Aliphatic and Related Natural Product Chemistry

4

R
0


(12) R = -NHCH2CHMe2
(13) R = -N

3

fuZvum12. This is believed to be the first report of polyacetylenic phytoalexins from the Solanaceae. Compound (17) has
subsequently been found in tomato plants infected with
13
Vertici lZium albo-atrum

.

0

gm-\

A number of new C I 3 compounds are reported. The isovalerate
(18) occurs in some Leucanthemum species along with many other
CarZina diae contains (19) and the carlina
acetylenic compounds’.
oxide derivative (20) in addition to other known compounds
including carlina oxide14. This is taken as confirmation of the
taxonomic reclassification of this species to the genus C a r Z i n a .
Three new thiophen chlorohydrins (21) - (23) are reported from
Pterocaulon virgatum15, along with two known compounds of this
type. The dithienylacetylene ( 2 4 ) has been isolated from


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Natural Acetylenic and Olefinic Compounds

5

Porophy Z Zurn r u d e r a Z e L 6 , and another dithienyl compound (25) occurs
17
in CaZea p i Z o s a

.

R

=

I

OH
( 2 1 ) R = Me
(22) R = H

I

OH

1

OA c

1


C1


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Aliphatic and Related Natural Product Chemistry

6

Two new C12 p h e n o l s ( 2 6 ) and ( 2 7 ) o c c u r i n L e u c a n t h e m u m
1
(34)
segetum
A m i x t u r e of seven new a r o m a t i c amides ( 2 8 )
C12 w a s i s o l a t e d from S p d Z a n t h e s
r a n g i n g i n c h a i n l e n g t h from C9
18
aZba

.

-

-

.

A number of Cl0 compounds r e l a t e d t o m a t r i c a r i a e s t e r a r e

r e p o r t e d . Baccharis q u i t e n s i s

t o r e l a t e d known compounds19.
( 3 7 ) - ( 4 0 ) w e r e i s o l a t e d from
The r a b b i t b r u s h
nauseosus**.

c o n t a i n s ( 3 5 ) and ( 3 6 ) i n a d d i t i o n
Four new m a t r i c a r i a e s t e r i s o m e r s
the rabbit brush, Chrysothamnus
i s a d e s e r t p l a n t , known t o be

r e s i s t a n t t o a t t a c k by t h e Colorado b e e t l e . The e x t r a c t e d m i x t u r e
of ( 3 7 ) - ( 4 0 ) was shown t o have an a n t i - f e e d a n t e f f e c t on t h e

I
R
bH

(26)

R

=

(27)

R

= H

Me


0

-

R2

1

( 2 8 ) R = Me

1

(29) R = H

H

0


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7

Natural Acetylenic and Olefinic Compounds
A I l g O/
W

(35)
0

0

AngO

'0

\

(36)

s
a
I
&
d
o
R

(37)

R

(38)

R = H

=

Ac


(37)]
(39)

R = Ac

(40)

R = H
OMe

HO-

\

0

R

(43)

A,,

R = OMe

(44) R = ANIi
(45)

R = 0 N
H+oMe


0


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Aliphatic and Related Natural Product Chemistry

8

beetle larvae and this type of naturally occurring compound is
suggested as an environmentally acceptable pest control agent.
Dimerostemma a s p e r a t u m contains two unusual lachnophyllum esters
(41) and (42)21. The fungus F a y o d i a b i s p h a e r i g e r a produces the
methyl ester ( 4 3 ) and the amide linked amino acid derivatives ( 4 4 )
and ( 4 5 ) which are the first reported compounds of this type22.
These structures were confirmed by synthesis.
Fuller details have now been published of the monoacetylenic
y-lactones described in the previous review23. The original
report described these as coming from L i c a r i a mahuba (Lauraceae),
but this plant h a s now been reclassified as CZinosternon mahuba.
2 . 3 Known Polyacetylenic Compounds from Terrestrial Plants.- A

large number of new sources of known polyacetylenic compounds have
been reported, mainly by Bohlmann and co-workers, often as an
offshoot of their studies on the Compositae terpenes. These new
sources are recorded in Table 1, along with the major compound
types isolated from them. Known compounds which were isolated
along with the compounds described in the previous section are
not included in the table.
Table 1 New sources of known acetylenic compounds within the

family Compositae
~

mown compound types

Species

Acritopappus s p p .
Agrianthus pmgens
Artemisia koidzumii
Baccharis spp.

24

‘13

25

‘13

‘14, 1 3 , 10

28

Centaurea canarienis

‘13-16

Chrysanthemum spp.


CI3, s p i r o enol e t h e r s

‘13

Echinops giganteus

C1

thiophen

‘13

clo
Cl0, C13 thiophen, d i t h i a n e

He Zichryswn auriceps

‘13
‘13

33
34

E A o p h y l l ~ ns p p .
Gnaphaliwn spp.
H . chionosphaem

30

32


EKgeron naudini

C13,

29

31

‘13

Doranicum hungalricwn
Eremanthus spp.

26
27

5 0

CaZea p i n n a t i f i d z

Conocliniopsis p r a s i i fo Zia

Reference

35

Chloro e n o l e t h e r s

36

37

38
39


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Natural Acetylenic and Olefinic Compounds
Table 1

9

Continued

Species

Known compound types

Reference

H. s e r p y l l i f o l i w n

C13, cyclic ether

40

Helichrysum spp.

C13, chloro enol ether, thiophen


41

Hymenoxys Z i n e a d f o l i a

‘17

Ichthyothere spp.
Leucanthemwn m a x i m

“13
C13, spiro enol ethers

Liabwn spp.

‘13

Libanothanmus spp.

‘13

Liguluria thyrsoidea

‘13

Matt f e ldanthus nobi 1i s

‘13

Morithamnus crassus


‘13

Onoseris albicans

‘13

P i p t o 1epis ericoide s

‘13

Plagiochei lus prostratus

‘10

Proteopsis argentea
Pulchea suaveoZens
Rhaponticwn carthmoides

‘1 3
C13, thiophen

Schkuhria s p p .

‘13
C13, thiophen, dithiane

Smallanthus fruticosus

‘13


S. uvedalia

‘13

So 1idago decurrens

‘10

Te l e kia speciosa

‘13

Vani 1losmopsis spp.

42
43

44
45
46

47

48
49
50
51
52


53
54
55
56

57
58
59
60
51

Verbesina spp.

‘13
C 1 3 ’ thiophen, dithiane

Vernonieae spp.

C13, thiophen

62

Wedelia t r i Zobata
WwzderZichia mirabilis

C 1 3 ’ thiophen

63

Zinnia spp.


‘13
‘4

7

61

64
65

1J

A useful method of visualising polyacetylenes on TLC plates

has been described. Vanillin and p-dimethylaminobenzaldehyde were
found to be the best reagents for locating a large variety of
polyacetylenes. The combination of RF and the colour produced
by the two spray reagents allowed twenty-five acetylenic compounds
to be distinguishedF6.
2 . 4 Acetylenic Compounds of Marine Origin.- A number

of acetylenic

compounds have been isolated from a variety of marine organisms,
including molluscs,sponges and seaweeds. The nudibranch mollusc


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Aliphatic and Related Natural Product Chemistry

10

DiauZuZa sandiegensis contains nine chlorinated C16 acetylenes,
These unstable compounds were easily extracted
(46) - (54)67.
from the intact mollusc and were separated by repeated reversephase liquid chromatography. The structures are based on
spectroscopic data, particularly 3 6 0 MHz 'H n .m.r spectra, and
some chemical transformations. Neither these compounds nor any
likely precursors were present in the sponges which form the
mollusc's diet, and it is suggested that the chloroacetylenes are
chemical defence substances.

.

(46)

1: , 3 E , 9 z

( 4 7 ) 1z , 3 2 , 9 z

(48)

15 , 3 E , 9 Z

( 4 9 ) 1Z , 3 2 , 9 %

( 5 0 ) lE , 3 E , 9 Z
( 5 1 ) 1Z ,3J",9Z


( 5 2 ) 12 , 3 Z ,9 2
( 5 3 ) 1F ,3F,9,7

The Mediterranean nudibranch P e l t o d o r i s a t r o m a c u Z a t a and its
prey, the sponge P e t r o s i a f i c i f o r r n i s , contain a number of common
metabolites and these have now been shown to include a number of
very lonq chain acetylenic compounds ( 5 5 ) and ( 5 6 1 6 % . These C71
t o C 8 9 compounds are believed to be the highest molecular weight
natural acetylenes known and they were isolated by reverse phase
h.p.1.c.
The structures followed from H
' and l3C n.m.r. spectra
and chemical transformations and the structure of the terminal
grouping was confirmed by synthesis. A complex mixture of


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Natural Acetylenic and Olefinic Compounds

11

p o l y a c e t y l e n i c a c i d s was a l s o i s o l a t e d , b u t n o t c h a r a c t e r i s e d .
P.

ficiformis i s normally red-brown due t o t h e p r e s e n c e of a

symbiotic alga.


Sponges of t h i s s p e c i e s l i v i n g i n d a r k c a v e s l a c k

t h e a l g a and a r e w h i t e .

I n a f u r t h e r s t u d y t h e s e w h i t e sponges

have r e v e a l e d t h e a c e t y l e n e s ( 5 7 )

-

(60) similar but not i d e n t i c a l

t o t h o s e found i n t h e c o l o u r e d sponges

HC = C C H C H = C H ~ - R ~ - CCH=CHC
H~

I

69

.

CCHC ICCH~-R~-CH~+H=CHCHC=CH

1

I

OH


OH
( 5 5 ) R1

+

R2

OH

(n

= CnH2n-B

( 5 6 ) R1 + R2 -

- CnH2n - 4

( 5 7 ) R1 +

R2

= CnHZn

-

= 25,28)

( n = 28,31,34)


(n = 2 6 , 2 9 )

HCECCH=CHCH2-R-CH2CECC0

2

CH

3

The r e d marine a l g a L i a g o r a f a r i n o s a c o n t a i n s t h r e e a c e t y l e n i c
lipids (61)
n.m.r.

-

(63I7O.

The s t r u c t u r e s a r e based on H
'

and o t h e r s p e c t r a .

and l 3 C

The compound ( 6 1 ) shows unexpected

a c u t e t o x i c i t y t o t h e r e e f - d w e l l i n g f i s h E u p o m a cen t ru s Z e u c o s t i c t u s .
( 6 3 ) i s a chronic t o x i n while (62) i s non-toxic.
A number of non-terpenoid


C15 a c e t y l e n i c m e t a b o l i t e s a r e known

from t h e r e d a l g a genus L a u r e n c i a .

These u s u a l l y show s t r u c t u r e s

c o n t a i n i n p c y c l i c e t h e r s and b e a r i n q halogen s u b s t i t u e n t s b u t a r e
b e l i e v e d t o be produced from a c y c l i c p o l y e n y n d i o l s .

Laureepoxide

( 6 4 ) i s a new compound of t h i s t y p e i s o l a t e d from L . n i p p o n i c a 71

.

The s t r u c t u r e and s t e r e o c h e m i s t r y of l a u r e n c i e n y n e (651, i s o l a t e d
from L . o b t u s a , have been determined by X-ray and s p e c t r o s c o p i c
The s t r u c t u r e of l a u r e n y n e ( 6 6 ) from t h e same s o u r c e
has s i m i l a r l y been determined73. The i n s e c t i c i d a l compounds

method^'^.

l a u r e p i n n a c i n ( 6 7 ) and i s o l a u r e p i n n a c i n ( 6 8 ) w e r e i s o l a t e d from