Connective Stereospecific Generation of Alkenes

NSF化学部的化学合成计划支持俄勒冈州立大学(OSU)化学系保罗·布莱克莫尔教授的研究。布莱克莫尔教授和他的学生正在探索一种制备烯烃的新方法，这是一类碳基分子。这些物质对包括医学、农业和工程在内的许多领域都有价值。烯烃可以以两种几何形式中的任何一种存在。由于这两种类型的烯烃具有不同的物理和生物特性，因此控制制备哪种形式的烯烃是至关重要的。在俄亥俄州立大学开发的化学反应使任一种几何形式的烯烃都可以选择性地生成。这项研究推进了从高中到本科、到研究生和博士后等不同经验层次的学生的教育。此外，Blakemore教授培养了来自传统上在物理科学中代表性较低的群体的学生的参与。这项研究介绍了一种基于富含对映体的SP3杂化卡宾的消除交叉偶联的立体控制烯烃合成的新方法。与不能完全控制立体化学的传统烯烃合成策略相比，本研究开发的方法不依赖于差异取代基来偏置一个异构体的生成。相反，在卡宾亚基中预先存在的绝对立体化学特征之间的相互作用被利用来引导碳-碳双键的形成朝向所需的立体异构体。为了探索这一新方法的范围，同时展示其与社会的相关性，与更简单的模型一起制备了含有生物活性化合物的复杂烯烃。其中包括P-糖蛋白刺激剂(治疗阿尔茨海默氏病的潜在药物)、维生素D3(一种具有多种用途的Secosterid)和PumilioToxin251D(一种具有钠离子通道活性的生物碱)。培养了下一代科学家。参加全州暑期实习项目的高中生被安排在布莱克莫尔教授的实验室里。

The Chemical Synthesis Program of the NSF Chemistry Division supports the research of Professor Paul Blakemore in the Department of Chemistry, Oregon State University (OSU). Professor Blakemore and his students are exploring a new method for the preparation of alkenes, a class of carbon-based molecules. These substances are of value to many fields including medicine, agriculture, and engineering. Alkenes can exist in either of two geometrical forms. It is essential to control which form of an alkene is prepared because the two types have different physical and biological properties. The chemical reactions developed at OSU enable either geometrical form of an alkene to be made selectively. This research advances the education of students spanning levels of experience from high school, to undergraduate, to graduate, and post-doctoral. In addition, Professor Blakemore foster the participation of students from groups that are traditionally underrepresented in the physical sciences.This research introduces a new approach for stereocontrolled alkene synthesis based on eliminative cross-coupling of enantioenriched sp3-hybridized carbenoids. By contrast to traditional strategies for alkene synthesis, which cannot wholly control stereochemistry, the method developed in this research does not rely on differentiated substituents to bias generation of one isomer over the other. Rather, interplay between pre-existing absolute stereochemical features within the carbenoid subunits is exploited to steer formation of the carbon-carbon double bond toward the desired stereoisomer. To explore the scope of this new method while demonstrating its relevance to society, complex alkene containing bioactive compounds are prepared alongside simpler models. These include a P-glycoprotein stimulator (a potential therapeutic for Alzeheimer's disease), vitamin D3 (a secosteroid with multiple applications), and pumiliotoxin 251D (an alkaloid with sodium ion channel activity). The next generation of scientists is nurtured. High school students participating in statewide summer internship programs are hosted within Professor Blakemore's laboratory.