Alta-ur-Rahman (Ed.) Studies in Natural Products Chemistry, Vol. 35
© 2008 Elsevier B.V. All rights reserved.
NOVEL DOMINO REACTIONS FOR SYNTHESIS
OF BIOACTIVE DITERPENOIDS AND
ALKALOIDS
SHANTA S. BHAR AND M.M.V. RAMANA
Department of Chemistry, University of Mumbai, Santacruz(E), Mumbai-
400098, INDIA
ABSTRACT: In the synthesis of relevant organic compounds such as natural products and
analogues, the proportion of the number of steps coupled with the increase of complexity
is now a universal paradigm to ascertain the quality and efficiency of a process. Alongwith
providing accessibility to a multitude of diversified classes of natural products such as
alkaloids, terpenoids, steroids and others, these criteria have been addressed by us via the
application of domino processes. The acid-catalyzed intermolecular cyclization has been
used as a viable synthetic tool for the stereospecific formation of different classes of
polycyclic natural products.
INTRODUCTION
The synthesis of bioactive natural products, agrochemicals,
pharmaceuticals have evolved to allow the formation of complex
molecules in a few steps, starting from simple substrates. Any synthetic
procedure involves either linear retrosynthesis or disconnection approach.
The linear pathway leads to a consecutive synthesis and the branching
pathway leads to a convergent synthesis. In a convergent synthesis, the
several pieces of a molecule are synthesized individually and the final
target is sequentially assembled from the fragments. In contrast, the
consecutive synthesis involves the stepwise formation of the final
complex molecule. It is apparent that the convergent synthesis will have
fewer consecutive steps in the overall synthesis (Chart-I) .
In a synthesis involving fifteen steps, if each step has a mean yield of
90%, the overall yield of final products is (0.9)15 "" 0.21 (21%). If the
largest sequence is split and divided into convergent solution, there would
be only four consecutive steps in a perfectly
convergent pathway. The yield of the final product would be (0.9)4"" 0.66
(66%). It is difficult, however to achieve such a perfect convergence,
since functional group manipulation, steric considerations, and asymmetry
lead to "imperfections" [I] .
An example of a convergent synthesis used by Fuchs[2] for the synthesis
of prostaglandin E
2
(PGE
2
) is illustrated in Chart-2, while an example of
consecutive synthesis used by Corey[3] for the synthesis of prostaglandin
E
2
(PGE
2
) is illustrated in Chart-3.
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