The Alkaloids: Chemistry and Pharmacology 44

391 Pages·1993·14.4 MB·English

by  Geoffrey A. Cordell (Eds.)

THE ALKALOIDS
Chemistry and Pharmacology
VOLUME 44
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THE ALKALOIDS
Chemistry and Pharmacology
Edited by
Geoffrey A. Cordell
College ofP/itirni~ii:v
University qf Illinois (11 Chicogo
C/2iCYZ~OI.I linois
VOLUME 44
Academic Press, Inc.
A Division ojH orcoiirt Brrrce & Cotnpntz>’
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This book is printed on acid-free paper. @
Copyright 0 1993 by ACADEMIC PRESS, INC.
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CONTENTS
CONTRIBUTOR.S.. ... ............................................ vii
PREFACE. ........... ............................................ ix
Chapter I. The Tropane Alkaloids
MAURIL OUNASMAAAN D TAIUAT AMMINEN
I. Introduction .............................. I
11. Occurrence .................................... 3
Ill. Synthesis ...................................... 78
IV. Reactions 89
92
95
................... 97
99
.............................................. I00
Chapter 2. The Biosynthesis of Tropane Alkaloids
RICHARDJ. ROBINSA ND NICHOLAJS. WALTON
I. Introduction ...................................................... I16
11. Organ Tissue Cultures for Biosynthetic Studies ............... I19
111. Formation of Putrescine ............................................ I30
IV. FormationofTropinone ............................................ 134
V. Formation of Tropine and Pseudotropine . 146
VI. Formation of Acidic Moieties of Tropeines ........................... 151
VII. Formation of Tropeines ........................... 155
VIII. Metabolism of Tropeines ......................... 160
IX. Degradation and Oxidation of Tropeines ............................. 164
X. Overall Regulation of Pathway ....................... 168
XI. Future Prospects ................................ I80
References ....................................................... I82
Chapter 3. Simple Indolizidine Alkaloids
HIROKTI AKAHATAAN D TAKEFUMMI OMOSE
I. Introduction ...................................................... 189
11. Indoiizidines with Alkyl and Functionalized Alkyl Appendages ......... 190
III. Elaeocarpus Alkaloids .............. ._. ............................ 22 I
V
vi CONTENTS
IV . Slaframine ........................................................ 223
V . Hydroxylated lndolizidines ......................................... 228
VI . Summary ......................................................... 250
References ....................................................... 250
Chapter 4 . Chemistry and Biology of Carbazole Alkaloids
D . P . CHAKRABORTY
I . Introduction ...................................................... 258
I1 . Occurrence ............ ................... 258
111 . Chemistry of Carbazole A loids ................................... 258
IV . Physical Properties of Carbazole Alkaloids ........................... 349
V . Biogenesis of Carbazole Alkaloids ................... .... 351
VI . Biochemical and Medicinal Properties of Carbazole AIka
Related Compounds ....... ....................... 352
References ............................................ .... 360
CUMULATIVINED EX OF TITLES. .......................................... 365
INDEX ................................................................. 373
CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors’ contributions begin
D. P. CHAKRABORT(2Y5 7), Institute of Natural Products, Calcutta 700
036, India
MAURLI OUNASMA(Al) , Laboratory for Organic and Bioorganic Chem-
istry, Technical University of Helsinki, SF-02150 Espoo, Finland
TAKEFUMMI OMOSE(1 89), Faculty of Pharmaceutical Sciences, Toyama
Medical and Pharmaceutical University, Toyama 930-01, Japan
RICHARDJ. ROBINS(1 15), Agricultural and Food Research Council Insti-
tute of Food Research, Norwich Laboratory, Colney, Norwich NR4
7UA, United Kingdom
HIROKTI AKAHAT(A18 9), Faculty of Pharmaceutical Sciences, Toyama
Medical and Pharmaceutical University, Toyama 930-01, Japan
TAIUAT AMMINEN(l ), Laboratory for Organic and Bioorganic Chem-
istry, Technical University of Helsinki, SF-02 150 Espoo, Finland
NICHOLAJS. WALTON( 1 IS), Agricultural and Food Research Council
Institute of Food Research, Norwich Laboratory, Colney, Norwich
NR4 7UA, United Kingdom
vii
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PREFACE
The scientific accomplishments of Professor Edward Leete, who con-
tributed so much to alkaloid chemistry and biochemistry during his bril-
liant and illustrious scientific career, are honored in this volume by two
chapters on the tropane alkaloids, an area of alkaloid research that was
especially dear to him. The format for the presentation of these two
chapters is new to this series. In Chapter I, Lounasmaa and Tamminen
provide a complete summary of the occurrence of the more than 200
tropane alkaloids characterized and also review the synthetic pathways
that have been developed for their formation.
In Chapter 2, Robins and Walton describe the tremendous progress that
has been made in the level of understanding of the intricate tropane al-
kaloid biosynthetic pathway. As is now revealed, seminally by Leete and
co-workers, the biosynthesis of the tropane alkaloids, particularly the
most infamous alkaloid, cocaine, is substantially more complex than origi-
nally envisaged. As details of these processes and the enzymes involved
are further studied and characterized, the intense subtlety of the pathways
is becoming apparent.
Takahata and Momose review the simple indolizidine alkaloids in Chap-
ter 3. These alkaloids are widely distributed in nature and some, such as
castanospermine (a potent glucosidase inhibitor), have been the subject of
intense synthetic and biological interest in the recent past.
Finally, in Chapter 4, the isolation, synthesis, and biological responses
of the carbazole alkaloids is reviewed by Chakraborty. Ranging from the
simple analogs present in Murraya species to the complex derivatives
found in certain fungi, the group displays a broad spectrum of structural
diversity and biological activity.
Geoffrey A. Cordell
University of Illinois at Chicago