Synthesis and Reactions of Carbene Boranes

项目概述在这个由化学系化学合成计划资助的项目中，匹兹堡大学化学系的Dennis P.Curran教授将探索小分子合成、聚合物合成和主族化学的目标。这项工作的概念和方法深化和拓宽了小分子合成的学科，并有助于提供其他学科所依赖的分子、材料和技术。这是在广泛关注可持续化学的情况下实现的，方法是使用常见的第二行元素硼(容易获得、无毒和可回收)来取代通常用于推动新反应发现的稀有、昂贵和/或有毒元素。该计划的特点是推进科学前沿和教学之间的强烈耦合，并培养不同的本科生和研究生群体。这些学生进入职场，成为推动许多领域进步的人力资本，这些领域对我们公民的健康和我们国家的经济至关重要。该项目还经常使用视频会议等尖端技术来管理洲际合作。这些合作将该提议的直接教学/培训影响从匹兹堡扩大到法国、日本和苏格兰。该提议的主要重点是开发新的基于硼的合成方法。许多工作集中在新发现的贫电子炔烃与N-杂环卡宾硼烷(NHC-硼烷)的双氢硼化反应上。这些反应提供了应变的硼烷(硼环丙烷)，并有机会发现构建功能化有机分子的新的、可持续的途径。正在研究这一不寻常的新反应的范围和机理，以及用碳-碳键和碳氧键取代产品中的NHC-硼烷基所需的化学物质。此外，NIH-二氟硼烷的开发工作正在进行中，这与这些中间体提供的形成新键的机会有关。

Project SummaryIn this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Dennis P. Curran of the Department of Chemistry at University of Pittsburgh will explore objectives in small molecule synthesis, polymer synthesis, and main group chemistry. The concepts and methods of this work deepen and broaden the disciplines of small molecule synthesis and help in the quest to provide the molecules, materials, and technologies that other disciplines rely on to progress. This is being accomplished with a broad focus on sustainable chemistry by using the common second row element boron (readily available, not toxic, and recyclable) to replace the rare, expensive and/or toxic elements typically employed to drive new reaction discovery. The program is characterized by a strong coupling between advancing the frontiers of science and teaching and training a diverse group of undergraduate students and graduate students. These students move into the workplace to become the human capital that drives progress in many areas that are vital to the health of our citizenry and the economy of our nation. The project also regularly uses cutting edge technology like videoconferences to manage intercontinental collaborations. These collaborations expand the direct teaching/training impact of the proposal beyond Pittsburgh to France, Japan and Scotland.The main focus of this proposal is the development of new boron based methods for synthesis. Much of the work centers on the newly discovered double hydroboration reaction of electron poor alkynes by N-heterocyclic carbene boranes (NHC-boranes). The reactions afford strained boriranes (boracyclopropanes) and an opportunity to discover new, sustainable pathways for the construction of functionalized organic molecules. The scope and mechanism of this unusual new reaction is being studied along with the chemistry needed to replace the NHC-borane group in the product with carbon-carbon and carbon-oxygen bonds. In addition, work toward the development of NIH-difluoroboranes is being pursued in connection with the opportunities for new bond formation that these intermediates afford.