Quantifying the Interplay of Structure and Reactivity in Ring Closing and Cross Metathesis

该计划将使用一些可合成的体系来提高我们对烯烃合环甲基化反应（RCM）和交叉甲基化反应（CM）有机反应机理的定量理解。我们希望确定有效摩尔浓度（em）作为环尺寸n和取代模式的函数，测量绝对环化和寡聚化率，并使用计算方法来理解这些数据。该计划将开发物理有机化学（实验动力学，计算方法）方面的专业知识和工具，同时研究具有相当重要基础意义和当前相关性的反应。我们建议协同使用计算和实验动力学技术来完善和/或挑战关于RCM反应机理方面的基本和一般想法，将反应纳入POC的专业领域。我们还希望发展有关交叉复合（CM）反应的补充见解，如果我们要充分了解围绕循环效率的问题，就需要这些见解。该计划的成功交付将显著推进研究知识，并为英国在烯烃复分解化学的重要和热门领域的地位做出相当大的贡献。

The proposed programme will use a number of synthetically accessible systems to improve our quantitative understanding of the organic reaction mechanism of the alkene ring closing methathesis (RCM) and cross metathesis (CM) reactions. We wish to determine effective molarities (EMs) as a function of ring size n and substitution patterns, to measure absolute cyclisation and oligomerisation rates, and to use computational methods to understand these data. The programme will develop expertise and tools in physical organic chemistry (experimental kinetics, computational methods) while investigating a reaction of considerable fundamental importance and acute current relevance. We propose to use computational and experimental kinetic techniques synergistically to refine and/or challenge fundamental and general ideas about aspects of the mechanism of RCM reactions, bringing the reaction within the domain of expertise of POC. We also wish to develop complementary insight concerning cross metathesis (CM) reactions, insights which are required if we are to understand the issues surrounding cyclisation efficiency fully. The successful delivery of this programme will advance research knowledge significantly and make a considerable contribution to UK standing in the important and topical field of alkene metathesis chemistry.