We are interested in how to apply a chemist's current knowledge about reactions and synthesis to new compounds. The knowledge-base we use can be found not only in recent journals, but in compilations in the form of databases of transformations which we adapt to organotin compounds, free radical reactions, ketyl intermediates, and non- cross-linked polystyrene support in organic synthesis. A significant part of our efforts are directed toward chemistry which combines two or more of these concepts in a single project. We have developed a new radical-anion triggered [3,3]- sigmatropic rearrangement using O-stannyl ketyls and we intend to develop this with other pericyclic reactions. Related to this work, our group has discovered a way to form tin enolates, which undergo many reactions of lithium enolates, by an entirely neutral free radical method which avoids bases like LDA. Standard tin reagents can also be mounted to polystyrene polymers which keeps toxic organotin contaminants out of reactions and results in cleaner products. This might lead the way for pharmaceutical companies to prepare almost tin-free products in free radical reactions.