Control of London Dispersion Interactions in Metal-Catalyzed C-H Activation

在这个项目中，我们将探索利用吸引伦敦色散能量相互作用来影响金属催化的碳氢功能化化学的活性和选择性。尽管最近在C-H功能化方面取得了相当大的进展，但关键的C-H激活的基本方面仍然知之甚少。因此，对催化剂形成和过渡态稳定的吸引伦敦色散能量相互作用的系统研究不幸的是尚未被证明是难以捉摸的。该计划将解决三个关键挑战，即(i) C-H活化的分散相互作用的量化，（ii）过渡金属催化的分散能供体DEDs的开发，以及（iii）通过分散相互作用对C-H键的非映对、元对和对映选择性活化的催化剂的合理设计。通过实验和计算机制研究对吸引色散相互作用的详细理解将刺激用于碳氢官能化及其他过渡金属催化的DEDs的发展。成功将完全依赖于制备化学、光谱学和理论家之间的紧密相互作用。因此，该项目将与协作网络中的其他活动产生强有力的相互作用。

In this project, we will explore the use of attractive London dispersion energy interactions to influence activity and selectivity in metal-catalyzed C–H functionalization chemistry. Despite of considerable recent advances in C–H functionalizations, fundamental aspects of the key C–H activation continue to be poorly understood. Thus, a systematic study on attractive London dispersion energy interactions for catalyst formation and transition-state stabilization has unfortunately as of yet proven elusive. This program will address three key challenges, namely (i) the quantification of dispersion interactions for C–H activations, (ii) the development of dispersion-energy donors DEDs for transition-metal catalysis, and (iii) the rational design of catalysts for the diastereo-, meta- and enantio-selective activation of C–H bonds through dispersion interactions. The detailed understanding of attractive dispersion interactions by experimental and computational mechanistic studies will stimulate the development of DEDs for transition-metal catalysis in C–H functionalizations and beyond. Success will entirely rely on a tight interplay between preparative chemistry, spectroscopy and theoreticians. The project will thus yield strong interactions with other activities in the collaborative network.