基于硫导向的非活化内烯烃的区域和立体选择性官能团化研究

Alkene functionalizations are a fundamental class of reaction with high atom-economic efficiency. However, challenges still remain in high-selective functionalizations of unactivated unsymmetrical internal alkenes because of the low reactivity of C-C double bond and difficult control of regio- and stereoselectivity. Directed transition metal catalysis has been one powerful tool for selective functionalization, but the requirement of special directing groups limits its more extensive utilization. It’s of great value to develop more atom-economically efficient directed transition metal catalysis and expand their employment in directed-regioselective functionalizations of unactivated internal alkenes. In this project, our research will focus on the high-regioselective hydrofunctionalizations and bifunctionalizaitons of sulfur-contained internal alkenes, which are rational to be achieved by using sulfur as the directing group for metal catalysis, and meantime, its electron-rich property to stabilize reaction intermediates. Assisted by appropriate chiral ligands, it could be easily developed to an efficient approach towards chiral organic sulfur compounds, which are important in various fields. Mechanism study would be another major part in this research, and we expect it could help promote the utilizations of the strategy, “self-containing heteroatoms as directing group”, in compounds synthesis and structure modifications, which have significant value and wide application foreground.

烯烃的官能团化是绿色高效的基本反应类型之一。由于双键较低的反应活性和难以控制的区域选择性和立体选择性，非活化不对称内烯烃的高选择性官能团化研究仍存在诸多挑战。导向的过渡金属催化已成为定位官能团化的重要工具，但导向基的引入需求在一定程度上限制了此策略的应用推广。研究和发展更为绿色高效的导向金属催化，并运用于非活化内烯烃的区域选择性官能团化，是非常值得研究的领域。本项目旨在通过利用硫原子对金属的配位导向作用，以及其富电子性对反应中间体的稳定作用，实现不同类型含硫内烯烃高区域选择性的氢化官能团化和双官能团化反应。并计划加以使用手性配体，为绿色高效合成手性含硫化合物提供一条便捷途径。同时也深入研究反应机理，推广“自身杂原子导向”这一经济且环境友好的策略在化合物合成和结构修饰中的应用，具有重要的研究价值和广泛的应用前景。

不饱和键官能团化反应中的区域和立体选择性控制是化学反应中的基本问题之一。本研究项目通过综合利用杂原子对金属的导向作用、以及参与试剂和金属配体的位阻作用，实现了多种碳碳不饱和键的区域和立体选择性官能团化反应，绿色高效合成了多类新颖的官能团化产物，为加深扩展杂原子导向功能的应用提供了理论和实验依据，为含杂原子化合物在医药、功能材料等领域中的应用研究提供了新的合成方法和素材，具有重大研究价值。