Pot-in-pot reactions: Heterogenization of homogeneous reaction processes for otherwise impossible cascades

Many excellent examples of homogeneous catalysts have been developed that elegantly and efficiently catalyze one reaction. Although the use of catalysts is ubiquitous in chemical synthesis, reactions must be carried out sequentially; else the catalysts/reagents may poison one another or require incompatible reaction conditions. These limitations make synthesis of vital molecules a tedious, expensive, and wasteful process. The process of multi-step synthesis is also not environmentally benign based on the sheer volume of waste generated per step. To overcome some of these limitations, catalysts have been site-isolated from each other therefore facilitating several steps in one reaction pot. However, available site-isolation methods have major shortcomings. Therefore, a general approach that works with already known chemistry and catalysts---without the need for further modification, is desired.;This thesis reports a new approach to catalyst site-isolation. We exploited the advantages of both heterogeneous and homogeneous processes to develop new cascade reaction sequences by employing polydimethylsiloxane thimbles as selective semi-permeable walls. These thimbles allow small organic molecules to diffuse through while retaining polar reagents and/or organometallic catalysts. A felicitous choice of reaction conditions led to the development of pot-in-pot reactions, a new concept in organic catalysis. To demonstrate how dynamic this new techniques is, we performed 2- and 3-step cascade reactions. This new approach circumvents the need to isolate intermediates, therefore enabling synthesis of otherwise challenging molecules. The genesis of our work was the occlusion of an organometallic catalyst in polydimethylsiloxane to perform catalysis in water. Also, by simply occluding the catalyst in a polymer matrix, it was possible to dictate whether the catalyst gave a metathesis or an isomerization product. Since the work summarized herein demonstrates site-isolation of a whole reaction process there was a need to redefine the term catalysis to accommodate the heterogenization of homogeneous reaction processes.