New Transition Metal Catalyzed Annulation Chemistry

本研究的重点是开发区域和化学控制的成环方法。 为了这些目的，将采用由区域控制的钯催化的烯炔-炔[4+2]苯并环化反应触发的共轭烯炔的顺序环加成/环化。 此外，将确定用于钯催化的[4+2]苯并环化反应的替代活化基团。 合成目标将包括2，5-二卡巴和2，4，5-三卡巴取代的间苯二酚核和氮杂类似物，以及用于单分散低聚亚苯基乙炔的单体。 氮杂-烯炔氮杂-烯炔亲物将用于通过过渡金属催化的[4+2]策略直接合成吡啶衍生物。有了这个奖项，有机和大分子化学计划支持了芝加哥伊利诺伊大学化学系的弗拉基米尔·格沃格扬博士的研究。 Gevorgyan博士将专注于金属催化形成多取代芳烃和杂芳烃的方法学开发。 这项研究将扩大过渡金属催化的成环反应的知识，并将为制备重要类别的化合物提供未充分利用的方法。 该项目为本科生和研究生的培训提供了一个极好的竞技场，并对制药行业产生了潜在的更广泛的影响。

The focus of this research is to develop regio- and chemocontrolled annulation methodologies. To these ends, sequential cycloadditions/cyclizations of conjugated enynes, triggered by regiocontrolled palladium-catalyzed enyne-yne [4+2] benzannulation reactions, will be employed. Further, alternative activating groups for the palladium-catalyzed [4+2] benzannulation reaction will be identified. Synthetic targets will include 2,5-dicarba-, and 2,4,5-tricarbasubstituted resorcinol cores and aza-analogs, as well as monomers for monodisperse oligophenyleneethynylenes. Aza-enyne aza-enynophiles will be used for the direct synthesis of pyridine derivatives via the transition metal-catalyzed [4+2] strategy.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Vladimir Gevorgyan of the Department of Chemistry at the University of Illinois at Chicago. Dr. Gevorgyan will focus his work on the development of methodologies for metal catalyzed formation of multisubstituted aromatics and heteroaromatics. The research will expand knowledge of transition metal-catalyzed ring forming reactions and will provide underemployed approaches for the preparation of important classes of compounds. The project provides an excellent arena for the training of undergraduates and graduate students and has potential broader impact for the pharmaceutical industry.