电化学条件下简单烷基腈类化合物的C(sp3)-H键官能团化的研究

有机腈类化合物是一类重要的含氮化合物，简单烷基腈的α位C(sp3)-H键官能团化是一种直接高效的合成有机腈类化合物的方法。传统的简单烷基腈碳氢键活化方法因通过烯醇化学产生碳属亲核试剂而需当量贵金属和强碱，近期通过碳属自由基的活化方法则需过量化学氧化剂及加热等条件，导致反应选择性低，可适用反应类型窄。本项目以电化学为技术进行简单烷基腈的C(sp3)-H键官能团化的研究。拟采用间接电合成法促使C(sp3)-H键活化以产生α-氰基碳自由基，其后续官能团化过程中的氧化还原步骤可借助电催化剂或者电极直接完成。该反应在常温，常压以及低电位下进行，其选择性易于调控。本项目将重点研究简单烷基腈的烯基化，以及过渡金属催化的与金属亲核试剂或含氮化合物的偶联反应。期望融合电催化和传统过渡金属有机催化过程，发展α-氰基碳自由基参与的新型反应，并阐明反应的深层机理，进一步发展高效、高选择性及对环境友好的合成新方法。

Organic nitriles are one group of the most important nitrogen-containing compounds. Functionalization of the C(sp3)-H bonds of simple alkyl nitriles is a direct and highly efficient way to construct complex organic nitriles. Early research efforts largely rely on the enol chemistry by using stoichiometric amounts of strong bases and transition metals. On the other hand, current methods involving nitrile–containing alkyl radicals need stoichiometric amounts of chemical oxidants and elevated temperature. These harsh reaction conditions result in low selectivity, limited type of transformation. In this proposal, electrochemical supported functionalization of the C(sp3)-H bonds of simple alkyl nitriles is studied. A redox catalyst is used to initiate the nitrile–containing alkyl radicals and the late stage of the reaction can also be assisted by the redox catalyst or the direct oxidation on the electrodes. Operated at room temperature, atmospheric pressure, and low oxidation potential, the selectivity of the reaction could be easily controlled. This work will focus on the study of alkenylation of simple alkyl nitriles, and the coupling reaction catalyzed by the transition metal with organic metal nucleophiles and N-nucleophiles. Here we propose that by merging the electrochemical catalytic process and transition metal organic catalysis, new reaction methodology involving nitrile–containing alkyl radicals will be developed. This new methodology provides a remarkably straightforward means of construction of new chemical bonds high efficiently, selectively and environmentally friendly.