Fortschritte der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products

596 Pages·1978·9.799 MB·English

by  Prof. Dr. O. R. Gottlieb, Prof. Dr. rer. nat. K. Herrmann, Dr. R. D. H. Murray, Dr. G. Ohloff, Prof. Dr. G. Pattenden (auth.), W. Herz, H. Grisebach, G. W. Kirby (eds.)

FORTSCHRITTE
DER CHEMIE ORGANISCHER
NATURSTOFFE
PROGRESS IN THE CHEMISTRY
OF ORGANIC NATURAL PRODUCTS
BEGRUNDET VON· FOUNDED BY
L. ZECHMEISTER
HERAUSGEGEBEN VON· EDITED BY
W. HERZ H. GRISEBACH G. W. KIRBY
TALLAHASSEE, FLA. FREIBURG i. BR. GLASGOW
VOL. 35
VERFASSER· AUTHORS
O. R. GOTTLIEB· K. HERRMANN· R. D. H. MURRAY
G.OHLOFF . G. PATTENDEN
1978
WIEN· SPRINGER-VERLAG· NEW YORK
This work is subject to copyright
All rights are reserved, whether the whole or part of the material is concerned, specifically those
of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying
machine or similar means, and storage in data banks
© 1978 by Springer-VerlagJWien
Library of Congress Catalog Card Number AC 39-1015
lSBN-13: 978-3-7091-8507-0 e-JSBN-13: 978-3-7091-8505-6
DOl: 10_1007/978-3-7091-8505-6
Inhaltsverzeichnis. Contents
Mitarbeiterverzeichnis. List of Contributors ..................................... VIII
Neolignans. By O. R. GOTTLIEB ............................................. I
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
II. S.S'-Neolignans. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1. 1,4-Diaryl-2,3-dimethyl-butene and butanes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2. 2,5-Diaryl-3,4-dimethyl-tetrahydrofurans and furans . . . . . . . . . . . . . . . . . . . . . 26
III. S.S',7.2'-Neolignans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . 30
1. I-Aryl-2,3-dimethyl-tetralins and naphthalene. . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2. 1,2-Dimethyl-I,2,4,6a,llb,llc-hexahydro-7-oxa-4-oxobenz Id el anthracene .. 34
IV. S.S',2.2'-Neolignans . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1. 6,7-Dimethyl-I,2,3,4-dibenzocycloocta-I,3-dienes ........................ 35
V. 3.3'-,5.1',2.2'- and 5.1',2.2',1.5',6.6'-Neolignans ........................... 37
1. 3,3' -Dipropenylbiphenyl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2. 3,3' -Diallylbiphenyls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3. Sa-Allyl-l ,2,3,4,5,6,5a,Sa-octahydro-I.4-(2' -allylethyleno)-2,6-dioxo-
naphthalene and internal cycloaddition product. . . . . . . . . . . . . . . . . . . . . . . . . 39
VI. S.3'-Neolignans. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
1. 2-Aryl-3-methyl-5-propenyl-2,3-dihydrobenzofurans . . . . . . . . . . . . . . . . . . . . . . 39
2. 2-Aryl-3-methyl-5-propenylbenzofurans ................................ 41
3. 5-Allyl-2-aryl-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans and
2,3,3a,6, 7, 7a-hexahydro-6-oxobenzofuran . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4. 2-Allyl-4-(~-methyl-~-styryl)-cyclohexa-2,6-dienone. . . . . . . . . . . . . . . . . . . . . . . 44
VII. 8.l'-Neolignans. . . . . . . . . . .. . . . . . . . . . . . . . . .. . . .. . . . . . . .. . . . . . . . . . . . . . . . . 45
1. 3a-Allyl-2-aryl-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans . . . . . . . . . . . . . 45
2. 3a-Allyl-2-aryl-3-methyl-2,3,3a,4,5,6-hexahydro-6-oxobenzofurans. . . . . . . . . . 47
VIII. Rearranged 8.1'-Neolignans. . . . . . . .. . . . . . . . . . . .. .. . . . . . . . . . . . . . . . . .. .. 49
I. 5-Allyl-2-aryl-3-methyl-2,3,5,6-tetrahydro-6-oxobenzofurans, 7-allyl-2-aryl-3-
methy 1-2,3,6,7 -tetrahydro-6-oxobenzofurans, 6-0-allyl-2-aryl-3-methyl-2,3-di
hydrobenzofurans, 7-allyl-2-aryl-3-methyl-2,3-dihydrobenzofurans and 7-
allyl-2-aryl-3-methylbenzofurans. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 49
2. l-Aryl-2-(p-allyloxyphenyl)-propane.................................... 50
IV Inhaltsverzeichnis. Contents
IX. 13C NMR Spectroscopy of Neolignans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 50
X. 8.1',7.3'- and 8.5',7.3'-Neolignans. . . . . . . . . . . . . . . . . . . . . .. . . .. . . .. . . . .. .. .. 52
I. l-Allyl-6-aryl-7-methyl-4-oxobicycio[3,2,I]oct-2-enes ..................... 52
2. l-Allyl-6-aryl-7-methylbicycio[3,2,I]octanes ......................... . . .. 53
3. 3-Ailyl-6-aryl-7-methyl-4-(and 8)-oxobicyclo[3,2,I]oct-2-enes . . . . . . . . . . . . . .. 54
XI. 8.1',7.9'-Neolignan. . . .. .. .. .. . ... . . . . . . .. . . . .. . . .. . . .. . . . . . . .. . . . .. .. .. 55
I. 2-Aryl-I-methyl-4,7-epoxy-9-oxo-~7.1o-spiro[5,5]undecane ........... '.. . . .. 55
XII. 8. O.4'-Neolignans ......................... . . . . . . . . . . . . . . . . . . . .. ... .. .. 56
I. l-Aryl-l-hydroxy-2-(p-E-propenylphenoxy)-propane. . . .. . . . . . . .. . . . .. .. .. 56
2. 7-Allyl-2-aryl-3-methylbenzodioxans ................................... 56
XIII. Function and Use of Neolignans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 58
XIV. Biogenesis of Neolignans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 59
XV. Conclusion ........... ,............................................... 64
Addendum .......................................................... ,..... 64
References .............................................................. 65
Hydroxyzimtsiiuren und Hydroxybenzoesiiuren enthaltende Naturstoffe in Pflanzen.
Von K. HERRMp,NN .................................................... 73
1. Einleitung ............................................................ 74
II. Hydroxyzimtsauren und Hydroxxbenzoesauren . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
III. Ester der Hydroxyzimtsauren und der Gallussaure mit anderen Hydroxycarbon-
sauren ............................................................... 80
1. Caffeyl-D-chinasauren (Chlorogensauren). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2. Dicaffeyl-D-chinasauren . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3. Ester der p-Cumarsaure, Ferulasaure, Sinapinsaure und Gallussaure mit China-
saure .............................................................. 83
4. Ester der Hydroxyzimtsauren mit Weinsaure ........................... 86
5. Ester der Hydroxyzimtsauren mit anderen Hydroxycarbonsauren .......... 86
IV. Verbindungen der Phenolsauren mit Kohlenhydraten ...................... 87
I. Ester der Hydroxyzimtsauren mit Mono-und Disacchariden . . . . . . . . . . . . . . 87
2. Weitere Ester der Hydroxyzimtsauren. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3. Ester der Hydroxybenzoesauren mit Mono- und Disacchariden ........... 91
4. Ester der Ferulasauren mit Polysacchariden ............................ 92
5. Glykoside der Phenolsauren .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
V. Ester der Hydroxyzimtsauren und Hydroxybenzoesauren mit n-Alkoholen,
n-co-Alkandiolen, Glycerin und co-Hydroxyfettsauren. . . . . . . . . . . . . . . . . . . . . . . 95
I. Ester mit Methanol und Athanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2. Ester mit langkettigen n-Alkoholen und n-co-Alkandiolen . . . . . . . . . . . . . . . . . 96
3. Ester mit Glycerin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4. Verbindungen der Hydroxyzimtsauren mit Hydroxyfettsauren . . . . . . . . . . . . . . 97
Inha1tsverzeichnis. Contents V
VI. Ester der Hydroxyzimtsauren und Hydroxybenzoesauren mit Naturstoffen auBer
Flavonoiden und G1ucosiden. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
1. Ester mit Cholin .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 98
2. Pheno1sauren mit Lignin ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 98
3. Ester der Feru1asaure mit Sterinen und Triterpenen ..................... 99
4. Ester mit Terpena1koho1en ........................................... 99
5. Ester mit Catalpol. .................................................. 100
6. Ester mit weiteren Naturstoffen und einige acylierte G1ykoside ........... 101
VII. Ester der Hydroxyzimtsauren und Hydroxybenzoesauren mit Pheno1glucosiden,
Cyc1ohexano1g1ucosiden und ahn1ichen Naturstoffen ....................... 102
1. Ester mit Arbutin (4-Hydroxypheny1-~-D-g1ucopyranosid) ................ 102
2. Ester mit Calleryanin (3-Hydroxy-4cO-~-D-glucopyranosy1-benzy1a1koho1) .. 103
3. Ester mit Salicin (2-0-B-D-G1ucopyranosy1-benzy1a1koho1) ................ 103
4. Ester mit Grandidentin (cis-2-Hydroxycyc1ohexyl-~-D-glucopyranosid) ..... 104
5. Acy1ierte 3,4-Dihydroxy-~-pheny1athy1-~-D-g1ucopyranoside .............. 105
VIII. Ester der Hydroxyzimtsauren und Hydroxybenzoesauren mit F1avonoiden .... 105
1. Ester mit Catechinen .................... .' ........................... 105
2. Ester mit F1avonen .................................................. 106
IX. Mit Hydroxyzimtsauren oder Hydroxybenzoesauren acy1ierte F1avonoidglykoside 107
1. Acylierte Anthocyanidinglykoside ..................................... 108
2. Acy1ierte F1avon( ol)glykoside ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3. Acylierte F1avanong1ykoside .......................................... III
X. Amide der Hydroxyzimtsauren und Hydroxybenzoesauren .................. 112
1. Verbindungen mit Aminosauren bzw. Proteinen ......................... 112
2. Amide mit Putrescin (1,4-Butandiamin) ................................ 113
3. Weitere Hydroxyzimtsaureamide ...................................... 113
XI. Isolierung, qualitativer Nachweis und quantitative Bestimmung ............. 114
XII. Bio1ogische Eigenschaften und Bedeutung ................................ 116
Literaturverzeichnis ..................................................... 118
Natural 4-YIidenebutenolides and 4-YIidenetetronic Acids. By G. PATTENDEN ....•.• 133
I. Introduction " . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 133
II. Structure and Distribution .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 134
1. 4-Ylidenebutenolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 134
2. 4-Y1idenetetronic Acids .............................................. 142
III. Synthesis ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 153
1. From 4-0xo-2-enoic Acids ............................................ 154
2. From Z-2-En-4-ynoic Acids ........................................... 158
3. From But-2-enolides ................................................. 161
4. From Substituted Maleic Anhydrides ................................... 165
5. Miscellaneous Syntheses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 168
VI Inhaltsverzeichnis. Contents
IV. Biosynthesis ........................................................... 171
I. Fungal Metabolites .................................................. 173
2. Pulvinic Acids and Pulvinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 177
3. Acetylenic Ylidenebutenolides in Compositae ............................ 181
4. Terpenoid Butenolides ............................................... 183
5. Other Metabolites ................................................... 187
V. Biological Activity ...................................................... 188
References .............................................................. 189
Naturally Occurring Plant Coumarins. By R. D. H. MURRAY. . . . . . . . . . . . . . . . . . . .. 199
I. Introduction: Scope of Review. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 200
II. Structural Types. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 201
I. Coumarins With Acyclic Substituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 201
2. Furano- and Pyrano-Coumarins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 201
III. Nomenclature......................................................... 203
IV. Isolation and Identification ............................................. 204
I. Isolation .......................................................... 204
2. Identification of Known Coumarins .................................. 206
2.1 Paper and Thin-Layer Chromatography ........................... 206
2.2 Gas-Liquid Chromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 206
2.3 High-Pressure Liquid Chromatography. . . . . . . . . . . . . . . . . . . . . . . . . . .. 206
V. Structure Determination ................................................ 206
I. Use of Spectroscopy ................................................ 207
1.1 Nuclear Magnetic Resonance Spectroscopy . . . . . . . . . . . . . . . . . . . . . . .. 207
1.2 Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 207
1.3 Ultraviolet and Infrared Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 207
2. Stereochemistry .................................................... 207
VI. Synthesis and Biosynthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 208
I. Synthesis.......................................................... 208
2. Biosynthesis ....................................................... 208
VII. Introduction to Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 209
Table I Coumarin and 7-0xygenated Coumarins ........................ 210
1.1 6-Substituted-7-0xygenated Coumarins . . . . . . . . . . . . . . . . . . . . .. 238
1.2 8-Substituted-7-0xygenated Coumarins . . . . . . . . . . . . . . . . . . . . .. 256
1.3 6,8-Disubstituted-7-0xygenated Coumarins .................. 298
Table 2 5,7-Dioxygenated Coumarins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 300
Table 3 6,7-Dioxygenated Coumarins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 322
Table 4 7,8-Dioxygenated Coumarins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 330
Table 5 5,6,7-Trioxygenated Coumarins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 344
Table 6 5,7,8-Trioxygenated Coumarins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 348
Table 7 6,7,8-Trioxygenated Coumarins ................................. 356
Table 8 5,6,7,8~Tetraoxygenated Coumarins ............................. 360
Inhaltsverzeichnis. Contents VII
Table 9 3-Substituted Coumarins ...................................... 362
Table 10 4-Substituted Coumarins ...................................... 368
Table 11 Miscellaneous Coumarins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 386
Formula Index ............................................................ . 393
Trivial Name Index ........................................................ . 395
References ............................................................... 400
Recent Developments in the Field of Naturally-Occurring Aroma Components. By
G.OHLOFF ............................................................ 431
I. Occurrence and Implication of Flavors .................................... 431
II. Oxygen-Containing Aliphatic Aroma Compounds .......................... 439
I. Alcohols and Carbonyl Compounds ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 439
2. Lactones ........................................................... 447
III. Isoprenoid Aroma Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 454
I. M onoterpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 454
2. Monoterpenoid Ethers and Lactones ................................... 468
3. Sesquiterpenes ...................................................... 471
4. Sesquiterpenoid Ethers . .'. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 479
5. Norsesquiterpenoids ................................................. 483
6. Metabolites From Higher Terpene Precursors ........................... 484
References ............................................................... 493
Namenverzeichnis. Author Index 529
Sachverzeichnis. Subject Index ............................................... 556
Mitarbeiterverzeichnis. List of Contributors
Gottlieb, Prof. Dr. O. R., Instituto de Quimica, Universidade de Sao Paulo, Caixa Postal
20780,01000 Sao Paulo, Brazil.
Herrmann, Prof. Dr. rer. nat. K., Lehrstuhl fUr Lebensmitte1chemie, Technische Universitat,
WunstorferstraBe 4, D-3000 Hannover, Bundesrepublik Deutschland.
Murray, Dr. R. D. H., Chemistry Department, The University, Glasgow GI2 8QQ,
Scotland.
Ohloff, Dr. G., Laboratoire de Recherches, Firmenich SA, Case Postale 239, CH-1211
Geneve 8, Switzerland.
Pattenden, Prof. Dr. G., Department of Chemistry, The University of Nottingham,
Nottingham, England.
Neolignans
By O. R. GOTTLIEB, University of Sao Paulo, Brasil
Contents
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
II. 8.8'-Neolignans........................................................ 24
1. 1,4-Diaryl-2,3-dimethyl-butene and butanes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2. 2,5-Diaryl-3,4-dimethyl-tetrahydrofurans and furans . . . . . . . . . . . . . . . . . . . . . 26
III. 8.8',7.2'-Neolignans . . . . . .. . . . . . . .. .. .. . . . . . . . . . . . .. . . . . . . . . . . . .. .. . . . . . 30
1. l-Aryl-2,3-dimethyl-tetralins and naphthalene. . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2. 1,2-Dimethyl-l,2,4,6a,1l b,llc-hexahydro-7-oxa-4-oxobenz I del anthracene .. 34
IV. 8.8',2.2'-Neolignans . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . .. .. . . . . . . .. . . . .. . .. .. 35
1. 6,7-Dimethyl-l,2,3,4-dibenzocycloocta-l,3-dienes ........................ 35
V. 3.3'-, 5.1',2.2'- and 5.1',2.2',1.5',6.6'-Neolignans ........................... 37
1. 3,3'-Dipropenylbiphenyl ....... , ........................ " .. . . . . . . . . . . 37
2. 3,3'-Diallylbiphenyls . .. . . . . . . . . . . . . . .. .. . . . . . .. . . . . . . . . . . . .. . . . .. . . .. 37
3. 8a-Allyl-l ,2,3,4,5,6,5a,8a-octahydro-l.4-(2' -allylethyleno)-2,6-dioxo-
naphthalene and internal cycloaddition product. . . . . . . . . . . . . . . . . . . . . . . . . 39
VI. 8.3'-Neolignans........................................................ 39
1. 2-Aryl-3-methyl-5-propenyl-2,3-dihydrobenzofurans . . . . . . . . . . . . . . . . . . . . . . 39
2. 2-Aryl-3-methyl-5-propenylbenzofurans ................................ 41
3. 5-Allyl-2-aryl-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans and
2,3,3a,6,7,7a-hexahydro-6-oxobenzofuran . .. . . .. .. .. . . . . . . . . .. . . . . .. .. .. 43
4. 2-Allyl-4-(~-methyl-~-styryl)-cyclohexa-2,6-dienone. . . . . . . . . . . . . . . . . . . . . . . 44
VII. 8.1'-Neolignans. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
1. 3a-Allyl-2-aryl-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans . . . . . . . . . . . . . 45
2. 3a-Allyl-2-aryl-3-methyl-2,3,3a,4,5,6-hexahydro-6-oxobenzofurans . . . . . . . . . . 47
Fortschritte d. Chern. org. Naturst. 35
2 O. R. GorrLIEB:
VIII. Rearranged 8.1'-Neolignans. ... ................. .. . .. ........ .. ....... 49
I. 5-Allyl-2-aryl-3-methyl-2,3,5,6-tetrahydro-6-oxo benzofurans, 7- allyl-2-aryl-3-
methyl-2,3,6, 7-tetrahydro-6-oxobenzofurans, 6-0-allyl-2-aryl-3-methyl-2,3-di
hydrobenzofurans, 7-allyl-2-aryl-3-methyl-2,3-dihydrobenzofurans and 7-
allyl-2-aryl-3-methylbenzofurans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2. l-AryI-2-(p-ailyloxyphenyl)· propane. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 50
. IX. 13C NMR Spectroscopy of Neolignans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 50
X. 8.1',7.3'- and 8.5',7.3'-Neolignans... .. .. .. .. ... ... ...... .. . .. .. .. .. ...... 52
1. l-Allyl-6-aryl-7-methyl-4-oxobicyclo[3,2,I]oct-2-enes ..................... 52
2. l-Allyl-6-aryl-7-methylbicyclo[3,2,I]octanes ... . . . . . . . . . . . . . . . . . . . . . . . . .. 53
3. 3-Allyl-6-aryl-7-methyl-4-(and 8)-oxobicyclo[3,2,I]oct-2-enes. . . . . . . . . . . . . .. 54
XI. 8.1',7.9'-Neolignan... ....... ..... .. . .. . .. ... . ... .. ... ......... .. ... .. .. 55
1. 2-Aryl-l-methyl-4, 7-epoxy-9-oxo-,17 .lO-spiro[5,5]undecane . . . . . . . . . . . . . . . .. 55
XII. 8.0.4'-Neolignans .... ... .. ..... .... ..... .. . ... ... ... .. .. ... .... ....... 56
1. l-Aryl-I-hydroxy-2-(p-E-propenylphenoxy)-propane.. . . . . . . . . . . . . . . . . . . .. 56
2. 7-Allyl-2-aryl-3-methylbenzodioxans ....... . . . . . . . . . . . . . . . . . . . . . . . . . . .. 56
XIII. Function and Use of Neolignans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 58
XIV. Biogenesis of Neolignans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .. 59
XV. Conclusion. . .. ... . . ... .. ... .. .. .. .... . ..... .... .. . .. .... . .. .. .. .. .. .. 64
Addendum ................................................................ 64
References .............................................................. 65
I. Introduction
According to HAWORlH (73, 74), lignans are plant products based
on carbon skeleta having two n-propylbenzene residues linked by the
~-carbon atoms of the side chains. Around 1940, when this definition was
published, practically all known bis-phenylpropanoids were derivatives
of structural variants of only 1 and 2 (Table 1). Since then, the
additional skeleta 3-15 were recognized and the restriction imposed
on the mode of union of the two units seems now unprofitable. It
was therefore proposed that the term lignan be extended to cover all
natural products of low molecular weight that arise primarily from the
oxidative coupling of p-hydroxyphenylpropene. units (106), a concept
which implicitly also refers to variants of skeleta such as 15 in which
the two units are linked by an oxygen· bridge. This is, of course,
fundamentally a biogenetic definition and· implies knowledge of the
monomeric precursor units.
Four such units seem to be involved: cinnamic acid (and exceptionally
aldehyde), cinnamyl alcohol, propenylbenzene and allylbenzene. These
are conveniently distributed among. groups, one encompassing the
References. pp. 65-72