This research will be supported by the Organic and Macromolecular Chemistry Program. The research will develop the chemistry of a class of sulfur containing molecules as a new synthetic pathway to the synthesis of molecules containing polycyclic systems. The development of these reactions will result in new methods for the preparation of the complex materials needed in medicine and agriculture. The chief objective of the research on the chemistry of unsaturated sulfones is to open up new synthetic methods for the preparation of unusual polycyclic ring systems. It is envisioned adding a variety of functionalized nucleophiles to phenylsulfonylallene followed by a subsequent base induced cyclization so as to prepare novel ring systems which could be of considerable use in organic synthesis. Substituted thiophenyl allyl sulfones undergo a 1,3-allylic sulfonyl shift and this process will be utilized within a metallation-alkylation sequence to prepare a variety of sulfonyl functionalized substrates. Other studies will deal with the recently uncovered ?3+2!-anionic cyclization of phenylsulfonyl-allene with methyl vinyl ketone. Since the ?3+2!-anionic cycloaddition strategy has not been investigated for the general synthesis of cyclopentenes, the cyclization reaction with a number of activated allenes and alkenes will be studied. Plans also include a study of the chemistry of diazafulvene, which it is believed can be generated as a transient species from the cycloadduct derived from diazomethane and phenylsulfonylallene. Another objective of the investigation will be to develop the chemistry of sulfonyl substituted cyclopropenes as reagents for the synthesis of some novel polycyclic ring systems.
