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Page 2

Bioorganic Marine
Chemistry Volume 6

Edited by Paul J. Scheuer

K.F. Albizati, V.A. Martin,
M.R. Agharahimi, D.A. Stolze

Synthesis of
Marine Natural Products 2
Nonterpenoids

With 161 Structures and 263 Schemes

Springer-Verlag
Berlin Heidelberg New York London
Paris Tokyo Hong Kong Barcelona Budapest

Page 166

156 Fatty Acid Derived Metabolites

Wittig olefination to produce the methyl ester of 22S-methyl-5,9-
octacosadienoic acid in 13 steps and 3 % overall yield. The enantiomer of 1801 is
prepared in a similar fashion.

4.4.8 Hexacosadienoic Acids

Djerassi has also prepared [492] the fatty acid (5Z,9Z)-5,9-hexacosadienoic acid
(1805) as shown in Scheme 317. Selective ozonolysis of 1,5-cyclooctadiene (1796),
tosylation, and reduction gives tosylate 1802 in which the two alkene substitu-
ents have been differentiated and the stereochemistry of the 9,10-double bond
has been set. Cuprate catalyzed coupling of tridecylmagnesium bromide with
tosylate 1802 yields the saturated sidechain. Wittig olefination of aldehyde 1804
provides the second double bond with correct geometry, thus giving 1805 in six
steps and 21 % yield. The cis-trans isomer was prepared in a similar manner,
involving olefin isomerization via the epoxide 1806. Treatment of 1806 with
lithium diphenylphosphide using a standard sequence gave the trans isomer
which was carried on to 1807 via a similar sequence. Scheme 317 also shows
syntheses of the other two diene isomers. Intermediate 1803 was converted to
the allylic alcohol 1808. Claisen rearrangement provided the trans geometry
about the new olefin in 1809. Chain elongation led to the desired 1810. Finally,
the all trans isomer 1812 was prepared from the trans acetal 1811 by an
analogous sequence.

1805

~COOH

~C13HzTn
1807

4.4.9 Diacetylenes from Reniera fulva

1810

Several long-chain diacetylenes containing a single propargylic stereocenter
from the sponge Reniera fulva [493] have been synthesized by Thaller [494] in
pure optically active form to confirm the assigned absolute configuration.
The routes are shown in Scheme 318 and require very little comment. The

Page 167

Miscellaneous Metabolites 157

° II
Me(CH2hCH =CH(CHz}9- C-(C=C)2

cis

H" pH
Me(CHz}sCH = CH(CHz}9 - ·C-(C =C)2CH20H

cis

Me(CH2ls-CH=CH(CHz}1O-(ClEC)2CH20H
cis

asymmetry at the carbinol carbon (70% ee) was produced by reduction of
an ex,~-alkynyl ketone with 9-BBN-(+)· ex-pinene complex. Based on the
known R-selectivity of this reagent, the absolute configuration was
confirmed.

Page 332

322 Subject Index

girolline 223-225
guanidine derivatives 210-225

halogenated l-octen-3-ones 256-258
hexaacetylce1enamide 59-63
hexacosadienoic acids 156
homoaerothionin 20
hormosirene, see dictyopterene B
hormothamnione 262-266
hybridalactone 106-107
hyellazole 175-179

indoles 158-175
isoindole 231-234

jaspamide 30-39
jasplakinolide, see jaspamide

allo-kainic acid 3-9
alpha-kainic acid 3-9
kjellmanianone 259

lamoxirene 129
latrunculin B 260-262
laurediols 71-74
laurencenyne 69-71
Laurencia haloethers 69-84
laurencin 74-78
laurenyne 78
leptosphaerin 250-253
lyngbyatoxin A, see teleocidins

malyngolide 279-294
cis-maneonenes 79
trans-maneonene B 79
manzamine C 188-192
7 -methoxy-1,6-dimethyl-5,8-dihydro-

isoquinoline-5,8-dione 234-237
1-methylisoguanosine 229-230
3-methylnavanone B 277-279
( + )-methylrhodomelol .249
mimosamycin 230-231
multifidene 121-125
mycalisine A 226-227

navanone A 192-193
nereistoxin 275-277
5-nonylpyrrole-2-carbaldehyde 243-244
Notheia anomala metabolite 146-147
nuc1eosides 226-230

octacosadienoic acids 147-156

okadaic acid 294-299
oroidin 220-223
ovothiol A 1-2
ovothiol C 1-2
6-imino-1,9-dimethyl-8-

oxopurine 228-229

pahutoxin 139-142
palythazine 257-261
panacene 84
patellamides 43-51
pentabromopseudilin 245-246
peptides 24-68
phidolopin 227-228
phosphonosphingoglycolipid 145
Plexaura metabolites 144-146
prec1avulone A 92-96
prostanoids 84-107
ptilocaulin 217-220
pukeleimide A 259-260
pulo'upone 193-195
punaglandin-3 102-106
punaglandin 4 96--102
(7E)punaglandin 4 102-106
punaglandins 96-106
pyridines 192-310
pyrogallol derivative 271-272
pyrrole derivatives 243-247

quinols 17-19

Reniera alkaloids 230-241
renierone 237-241
( + )-rhodomelol 249

saxitoxin 211-216
serenin, see dictyopterene D'
surugatoxins 158-165

teleocidin A-I 63-68
te1eocidin A-2 63-68
tetraacetylc1ionamide 13-14
tetrahalogenoindoles 173
tetrodotoxin 210-211
trikentrins 165-169

ulicyc1amide 51-54
ulithiacyc1amide 51-54

viridiene 125-128

3-octadecyl pyrrole-2-carbaldehyde 243 zoanthoxanthins 241-243

Page 333

P.J.Scbeuer, University of Hawaii at Manoa (Ed.)

Bioorganic Marine Chemistry

K. F. Albizati, V. A. Martin, M. R. Agharahimi, D. A. Stolze,
Wayne State University, Detroit, MI

Volume 5

Synthesis of Marine Natural Products 1
Terpenoids
1991. Approx. 220 pp. Hardcover ISBN 3-540-54375-9

Volume 6

Synthesis of Marine Natural Products 2
Nonterpenoids
1991. Approx. 270 pp. Hardcover ISBN 3-540-54376-7

These reviews are devoted to a compilation of the domain of natural
product synthesis that involves metabolites from marine organisms.
The vast amount of material has been roughly organized along
structural-biogenetic lines into two
volumes: the first covers all terpenoid
derived structures, the second nonterpenoid
(amino acid, heterocyclic, fatty acid and
other miscellaneous derived) metabolites.
For each metabolite the source is discussed
and some of the properties are described
that make the compound attractive to
synthesis chemists. These are mainly the
substances' biological activities.

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