Frontiers in Olefin Metathesis & Metathesis-Derived Nanomaterials

烯烃复分解是目前已知的构建新的碳-碳键和新分子框架的最强大、最通用的方法。它的应用范围从新药物的组装到可再生资源的利用，正如2005年诺贝尔奖所引用的那样。在制药和特殊化学品制造领域的应用，人们预计了几十年，这是最近才出现的现实。复分解被用于获取新的、有效的病毒抑制剂，并将可再生植物油转化为特殊化学品。******尽管有巨大的潜力，但主要的限制仍然阻碍了它的使用，特别是在化学制造方面，它有可能大大减少浪费。一个主要的挑战在于促成这些反应的催化剂的寿命很短。这导致了不经济、不可靠的过程：此外，相互竞争的反应会产生副产品。这严重限制了可再生植物油原料转化的复分解的实际应用，并且在制药公司的报告中被强调为一个严重的，反复出现的问题。******我们在这一重要领域的大部分工作都是为了理解和解决限制催化剂寿命和生产力的因素。我们试图了解为什么这些催化剂是脆弱的，以及它们在使用条件下如何分解。这种理解将有力地帮助我们设计下一代长寿命催化剂，并扩大工业应用。我们还寻求扩大这些能力，使目前无法实现的分子结构组装成为可能。开发强大的、通用的、易于处理的催化剂将使这些强大的分子设计工具发挥其长期以来的潜力。******最后，我们也在研究利用催化剂分解的大胆的新可能性。我们最近发现，纳米颗粒的形成是分解的关键项目。通过学习如何阻碍或促进这些反应，我们希望在分子和纳米颗粒催化的前沿创造重大机会。

Olefin metathesis is the most powerful and versatile method now known for building new carbon-carbon bonds, and hence the frameworks of new molecules. Its applications range from the assembly of new drugs to utilization of renewable resources, as cited in the Nobel Prize for metathesis in 2005. Uptake in pharmaceutical and specialty-chemicals manufacturing, anticipated for decades, is a very recent reality. Metathesis is being used to access new, potent viral inhibitors, and to transform renewable plant oils into specialty chemicals.******Despite its enormous potential, however, major limitations still impede its use, particularly in the context of chemical manufacturing, where it has the potential to dramatically reduce waste. A major challenge lies in the short lifetimes of the catalysts that enable these reactions. This leads to uneconomic, unreliable processes: moreover, competing reactions lead to byproducts. This severely restricts the practical use of metathesis for transformation of renewable plant-oil feedstocks, and has been highlighted as a serious, recurring problem in reports from pharma. ******Much of our work in this important area is directed at understanding and addressing the factors that limit catalyst lifetimes and productivity. We seek to understand why these catalysts are vulnerable, and how they decompose under conditions of use. Such understanding would be a powerful aid to designing next-generation, long-lived catalysts, and expanding industrial uptake. We also seek to expand these capabilities, to enable the assembly of molecular structures presently unattainable. Development of robust, versatile, readily-handled catalysts would allow these powerful tools for molecular design to reach their long-heralded potential. ******Finally, we are also investigating bold new possibilities in which we harness catalyst decomposition. We have recently discovered that nanoparticles are formed as key projects of decomposition. By learning how to impede, or promote, these reactions, we hope to create major opportunities at the forefront of molecular and nanoparticle catalysis.