Oxygenated Carbenoids for Stereospecific Reagent Controlled Homologation

该奖项是根据2009年《美国复苏和再投资法案》(公法111-5)提供资金的。支持的研究将建立在早期发现的关于对映体富集型主基手性卡宾对硼酸酯衍生物的立体特异性试剂控制同系化(STRECH)的基础上。STRECH使立体化学复杂分子的可编程迭代合成成为可能，但到目前为止，这一方法仅成功地用于聚烷基化材料的精制。将开展旨在扩大STRECH范围以涵盖多氧分子合成的研究。在这一努力中，将研究两种能够引入氧合的规模化类卡宾物种：α-金属环氧烷和α-金属S，O-缩醛。将探索产生这些敏感的有机金属试剂的新方法，并将使用它们的STRECH过程战略性地部署到具有代表性的生物碱和聚酮天然产物的全合成中。通过这一奖项，有机和高分子化学计划支持俄勒冈州立大学化学系保罗·R·布莱克莫尔教授的研究。布莱克莫尔教授致力于开发实现立体控制有机合成的新方法和新概念。通过瞄准促进分子构建的工具的开发，这项研究最终将通过加速发现生物活性物质和其他潜在有用的碳基材料而造福于整个社会。

This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5). The supported research will build on earlier discoveries concerning the stereospecific reagent controlled homologation (StReCH) of boronic ester derivatives by enantioenriched main group chiral carbenoids. StReCH enables a programmable iterative synthesis of stereochemically complex molecules, but to date this methodology has only been successfully demonstrated for the elaboration of polyalkylated materials. Studies designed to widen the scope of StReCH to encompass the synthesis of polyoxygenated molecules will be undertaken. In pursuing this endeavor, two types of scalemic carbenoid species capable of introducing oxygenation will be investigated: alpha-metallated oxiranes and alpha-metallated S,O-acetals. New methods for the generation of these sensitive organometallic reagents will be explored and StReCH based processes employing them will be strategically deployed for the total synthesis of representative alkaloid and polyketide natural products.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Paul R. Blakemore of the Department of Chemistry at Oregon State University. Professor Blakemore's research efforts focus on the development of new methods and concepts for the achievement of stereocontrolled organic synthesis. By targeting the development of tools that facilitate molecule building, the research will ultimately benefit society at large by speeding the discovery of biologically active agents and other potentially useful carbon based materials