Design and Serendipity in the Synthesis

Winpenny, Richard E.P., Design and Serendipity in the Synthesis of Polymetallic Complexes of the 3d-Metals, 5, 193. 

Winpenny, R.E.P. (1999) Design and serendipity in the synthesis of polymetallic complexes of the 3d-metals. Perspectives in Supramolecular Chemistry, 5 (Transition Metals in Supramolecular Chemistry) 193-223. 

Currently the main interest in template reactions lies in their key role in the controlled synthesis or the self-assembly of a variety of supramole-cular entities (449). One needs a combination of intuition, conjecture, and serendipity (450) a recent example of successfully combining serendipity and rational design is provided by the silver(I)-promoted assembly of one-dimensional stranded chains (451). One also needs an understanding of mechanism in order to optimize the selection and design of building blocks and templates for the generation of yet more sophisticated supramolecular structures references cited in this present review contain at least some kinetic or mechanistic information or speculation. Template routes to interlocked molecular structures have been reviewed (452), while a discussion of switching by transition metal contains a little about the kinetics and mechanisms of this aspect of template... 

In the early days of automated synthesis there was a fear amongst researchers that it would reduce the chances of serendipity. However, experience has now shown that, when used in sensible way, the, automation of the design, synthesis and test cycle can increase significantly the odds of chance discoveries of new compound that have attractive properties to the company in unforeseen ways. 

Natural product synthesis, can lead to the discovery of new reactions by chance, by open-eyed serendipity, or by design. Our total synthesis of ionomycin (Scheme 6) [45] led us in fact to consider a design-based approach for the construction of deoxypropionate, and propionate subunits which are the natural building blocks for a large number of macrolide and ionophore-type antibiotics [46]. 

The syntheses of [4], [5], and [6]rotanes as well as precursors for those of [7] and [8]-rotanes have been recorded in a full paper 34. In another synthetic study of rotane synthesis employing ring enlargement of certain ketonic intermediates, led perhaps by design, perhaps with the intervention of serendipity, to compounds such as 88 35. ... 

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