Unsaturated Sulfones in Organic Synthesis (Chemistry)

本研究将由有机与大分子化学计划资助。本研究将开发一类含硫分子的化学性质，为含多环体系分子的合成开辟一条新的合成途径。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。不饱和砜化学研究的主要目的是为非常规多环体系的制备开辟新的合成方法。设想将各种功能化的亲核试剂添加到苯基磺酰亚烯中，然后进行碱诱导环化，以制备可在有机合成中有相当用途的新型环体系。取代噻吩基烯丙基砜发生1,3-烯丙基磺酰基转移，该过程将在金属-烷基化序列中用于制备各种磺酰基功能化底物。其他研究将处理最近发现的ı3+2！苯基磺酰基烯与甲基乙烯酮的阴离子环化。自从ı3+2！一般合成环戊烯的-阴离子环加成策略尚未研究，将研究与一些活化的烯和烯烃的环化反应。计划还包括对重氮富尔芬的化学研究，据信，重氮富尔芬可以从重氮甲烷和苯磺基亚烯衍生的环加合物中作为一种瞬态物质生成。研究的另一个目的是发展磺酰基取代环丙烯的化学性质，作为合成一些新的多环体系的试剂。

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.