Unsaturated Sulfones in Organic Synthesis (Chemistry)

这项研究将得到有机化学和高分子化学项目的支持。这项研究将发展一类含硫分子的化学，作为合成含有多环体系的分子的一条新的合成途径。这些反应的发展将导致制备医药和农业所需的复杂材料的新方法。不饱和磺酸化合物化学研究的主要目的是为制备特殊的多环环体系开辟新的合成方法。人们设想在苯磺酰基烯上加入各种官能化的亲核试剂，然后进行碱诱导环化反应，从而制备出在有机合成中有相当大应用的新型环系。取代的苯硫基烯丙基砜经过1，3-烯丙基磺酰转移，这一过程将在金属-烷基化序列中用于制备各种磺酰基底物。其他研究将涉及最近发现的苯磺酰丙二烯与甲基乙烯基酮的ı3+2！-阴离子环化反应。由于ı3+2！-阴离子环加成反应还没有被用于一般环戊烯的合成，因此我们将研究它与一些活性烯和烯烃的环化反应。计划还包括对二氮富烯的化学进行研究，据信它可以作为一种瞬时物种从重氮甲烷和苯磺酸烯衍生的环加成物中生成。研究的另一个目标是发展磺酰取代环丙烯的化学，作为合成一些新的多环环体系的试剂。

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 ı3+2!-anionic cyclization of phenylsulfonyl-allene with methyl vinyl ketone. Since the ı3+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.