Metal-Catalyzed Silylene Transfer Reactions as Methods for the Synthesis of Strained trans-Cycloalkenes

在这个由化学合成计划资助的项目中，纽约大学的Keith Woerpel教授开发了含硅活性中间体的新化学反应，以合成一类特别难制备的化合物--反式环烯烃，并探索了这类化合物的化学。这一困难的根源是它们的能量非常高，这使得它们非常活跃，很难使用传统方法进行分离。相反，它们独特的反应性使这些诱人的中间体用于合成具有生物活性的化合物和其他有用的化合物。一旦确定了这种特定类型化合物的反应性，就可以预测结构相关化合物的结构和反应性，并可以开发药物、探索生物系统的工具、用于医疗和技术应用的塑料以及太阳能电池材料的设计和合成。该项目还为研究生、本科生和预科学生提供培训工具，为他们在研究、医学和材料科学方面的职业做准备。二价硅活性中间体(硅烯，R2Si)用于制备高度应变的反式环烯烃。尽管应变环烯烃在开发合成生物活性天然产物的有效路线方面有希望，但构建应变环烯烃一直是困难的。这个项目探索了高度应变的七元环和八元环反式烯烃的合成，并检验了这些化合物的反应活性的提高。对这些化合物的新反应的研究集中在产生用其他方法难以制备的产品的反应上。更多的努力将解决新反应的详细反应机制，这些反应明显偏离预期的反应性。

In this project, funded by the Chemical Synthesis Program, Professor Keith Woerpel of New York University develops new chemical reactions of silicon-containing reactive intermediates to synthesize a class of compounds, trans-cycloalkenes, that have been particularly difficult to prepare, and explores the chemistry of this class. The source of that difficulty has been their extraordinarily high energy, which renders them very reactive and difficult to isolate using conventional methods. Conversely, their distinctive reactivity makes these tempting intermediates for the synthesis of biologically active and other useful compounds. Once the reactivity of this particular type of compound has been determined, the structure and reactivity of structurally related compounds can be predicted, and the design and synthesis of pharmaceutical agents, of tools for exploring biological systems, of plastics for use in medical and technological applications, and of materials for solar cells can be exploited. This project also serves as a training tool for graduate, undergraduate, and precollege students to prepare themselves for careers in research, in medicine, and in materials science.Divalent silicon reactive intermediates (silylenes, R2Si) are used to prepare highly strained trans-cycloalkenes. Although strained cycloalkenes show promise for the development of efficient routes for the synthesis of biologically active natural products, the construction of strained cyclic alkenes has been difficult. This project explores the synthesis of highly strained seven- and eight-membered ring trans-alkenes and examines the elevated reactivity of these compounds. Studies of new reactions of these compounds focus on reactions that give products that are difficult to prepare using other methods. Additional efforts will address the detailed reaction mechanisms of new reactions that deviate significantly from expected reactivity.