Novel Catalytic Annulation Chemistry

在这个由化学系化学合成计划资助的项目中，伊利诺伊大学芝加哥分校化学系的Vladimir Gevorgyan教授将开发过渡金属催化的多取代芳烃和杂芳烃方法。虽然存在几种构建苯环的方法，但已知的催化过程存在区域选择性问题。更具选择性的方法需要使用化学计量的有机金属试剂，因此严重限制了这些方法的广泛应用。这些限制将在拟议的项目中通过开发高效的Pd催化的[4+2]和形式[2+2+2]苯环反应来解决，以实现多取代苯环的区域选择性组装。对新的苯环前后级联变换的研究将极大地扩展这一方法论的范围。这项拟议的研究处于有机金属和有机化学与催化的交界处，还将提供本科生和研究生水平的多学科培训。此外，Gevorgyan教授还积极致力于促进STEM学科中妇女的职业发展。拟议的工作预计将在健康相关领域产生更广泛的影响，因为它提供了通往具有生物重要性的中间体的新的有效途径，并使材料科学能够方便地获得有价值的构件，这些构件可用于复杂框架和结合材料的快速组装。此外，这里提出的“一锅反应”的发展可以降低化学产品的成本，避免化学废物的产生，具有经济和环境影响。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Vladimir Gevorgyan of the Department of Chemistry at the University of Illinois at Chicago will develop transition metal-catalyzed methodologies towards multi-substituted aromatics and heteroaromatics. Although several methods for construction of benzene rings exist, the known catalytic processes suffer from regioselectivity problems. More selective methods require employment of stoichimetric organometallic reagents, thus severely limiting broad application of these methodologies. These limitations will be addressed in the proposed project through the development of highly efficient Pd-catalyzed [4+2] and formal [2+2+2] benzannulation reactions toward regioselective assembly of a multisubstituted benzene ring. Studies toward new pre- and post-benzannulation cascade transformations will dramatically expand the scope of this methodology. The proposed research, which is at the interface of organometallic and organic chemistry and catalysis, will also provide multidisciplinary training at the undergraduate and graduate level. In addition, Professor Gevorgyan is actively engaged in promoting careers for women in the STEM disciplines. The proposed work is expected to have broader impacts in the health related area by providing new effective routes to biologically important intermediates, and in materials science by allowing easy access to valuable building blocks, which could be utilized in the rapid assembly of complex frameworks and conjugated materials. Moreover, the herein proposed development of "one-pot reactions" may reduce the cost of chemical products and avoid the production of chemical waste, providing both economical and environmental impacts.