-CHAPTER2-

THE STRYCHNOS ALKALOIDS

JOAN BOSCH,JOSEP BONJOCH,

AND MERCEDES
AMAT
Laboratory of Organic Chemistry, Faculty of Pharmacy
University of Barcelona
08028 Barcelona, Spain

I. Introduction and Scope ..................

11. Occurrence and Structures
111. Synthesis ...................
A. Closure of Ring C ..
B. Simultaneous Formation o
C. The Intramolecular Diels-Alder Approach for Rings C, D, and E .......... 152
D . Closure of the Piperidine Ring ................. 158
E. Closure of the Carbocyolic E Ring ................................................... 169
170
181

I. Introduction and Scope

Among the numerous indole alkaloids derived from secologanin and

tryptophan, the Strychnos type includes those alkaloids in which an unre-
arranged monoterpenoid unit may be identified as being attached to the
indole nucleus by C-2-C-16 and C-7-C-3 (or -C-21) bonds ( I ) .
These alkaloids are found only in species of the plant families Apocyna-
ceae and Loganiaceae (2-4) and are biogenetically formed via geissoschi-
zine and preakuammicine, either directly from the latter (Strychnan skeletal
type; C-7-C-3 bond) or via the intermediacy of stemmadenine-related imi-
nium cations (Aspidospermatan skeletal type; C-7-C-21 bond) (Scheme
1) (495).
Hence, two main skeletal types of Strychnos alkaloids, depending on the
location of the two-carbon (C-18-C-19) chain, may be identified. According
to Hesse’s classification (2,3),these skeletal types can be further subdivided
on the basis of the variations of their basic carbon skeleton (6,7).
Throughout this chapter the numbering system and ring labeling
(ABCDE) based on the biogenetic interrelationship of indole alkaloids, as
proposed by Le Men and Taylor (8),is used.
THE ALKALOIDS, VOL. 48
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Copyright 0 1996 by Academic Press, Inc.
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