双金属协同活化碳硼烷B-H键及其应用潜能

项目名称： 双金属协同活化碳硼烷B-H键及其应用潜能

项目编号： No.21472086

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 燕红

作者单位： 南京大学

项目金额： 90万元

中文摘要： 碳硼烷衍生物在能源，国防，医药，核污染处理，耐高温材料等领域有着非常重要的应用，由此衍生出的碳硼烷修饰化学拓宽了此类物质的应用范围。一般而言，碳硼烷的主要修饰在碳原子上，因为碳硼烷B-H极性小，难以活化，而且众多化学环境相近的硼位点的选择性修饰一直是合成的挑战。该申请首次提出了通过双金属协同作用实现碳硼烷B-H键的选择性活化及功能化，包括双金属协同诱导的分子内B-H活化机理的研究，以及由此机理推广为双金属催化（即分子间）的碳硼烷的选择性功能化，后者为一条简单，实用，高效，绿色的途径。通过碳硼烷B-H功能化新方法获得的具有特定官能团或药效团的化合物用于生物学以及医学的研究，如用于当前在BNCT(硼中子捕获疗法)抗癌药物研究中药物分子的靶向性问题，以及癌细胞的耐药性问题，预期揭示抑制癌细胞耐药性的机理。

中文关键词： 过渡金属；反应性；B-H活化；生物活性

英文摘要： Carborane derivatives have been widely investigated owing to their important applications in materials, energy, defence and pharmaceutical and nuclear wast recycling. The varity of the applications is dependent on the versatile chemical modifications of carboranes. So far, the chemical modifications of carboranes have been well established on the C-H bonds, however, the B-H activation has proved difficult becouse of the inert B-H bonds. Especially, the selective B-H activation has been the synthetic challenge. Here we firstly proposed to realize selective B-H bond functionalization at boron vetexes of carborane via metal-metal coorperation. This proposal contains intramolecular induced B-H bond activation at bimetallic centers including the study on the activation mechanism. We also wish to achieve catalyzed B-H bond activations via an intermolecular pathway by rational design of bimetallic catalysts, which stands for a proctical and efficient pathway. Finally, the aim to invent these new synthetic methods is to obtain new candidate compounds for biological and medical studies, including BNCT drug design and drug-resistance invetigation in cancer treatment.

英文关键词： transition metal;reactivity;B-H activaiton;biological activity