过渡金属催化的 “借官能团”反应

The transition-metal-catalyzed “borrowing hydrogen” reactions with the high atom-economy have been well developed in recent years, and various transition-metal catalyst systems, challenging substrates, and new reaction processes have been documented. The "borrow and return" strategy can improve the atomic utilization of the reaction, however, to the best of our knowledge, the functional group in this “borrow and return” reaction was limited to the hydrogen atom, the other functional group such as cyano or alkynyl is not tolerant, which restricts the scope of this “borrow and return” strategy. Therefore, this project is devoted to using the similar "borrowing hydrogen" reaction process to realize the "borrow and return" of various functional groups and expand the scope with the introduction of the concept of "borrowing functional group". This project will develop a series of “borrowing functional group” reaction, such as “borrowing cyano” reaction with cyano as the functional group and “borrowing alkynyl” reaction with alkynyl as the functional group. We will explore the effective catalyst system for the “borrowing functional group” reaction and disclose the reaction mechanism. The “borrowing functional group” reaction will provide a new idea for the activation of functionalized compounds and a new strategy for metal-catalyzed organic synthesis reactions.

近年来，原子经济性好的过渡金属催化“借氢”反应取得了卓越的成果，报道了各种过渡金属的催化体系，具有挑战性的底物以及新的反应过程。用“借和还”策略的反应能提高反应的原子利用率，但是就目前情况看，“借和还”只限于氢原子，而对于各种官能团的“借和还”却没有涉猎，极大地限制了这类反应的适用范围。为此，本项目拟运用与“借氢”反应相似的反应过程及原理，实现各种官能团的“借和还”的反应，拓展此类反应的适用范围，并由此引入“借官能团”反应的概念。本项目将开发一系列的“借官能团”反应，如以氰基为官能团的“借氰”反应和以炔基为官能团的“借炔”反应等，探索能够催化此类“借官能团”反应的催化体系，并深入的研究其反应过程及反应机理。通过本项目的研究，为含有官能团结构的化合物的活化提供一种新的思路，同时也为金属催化的有机合成反应提供一种新策略。

我们开展过渡金属催化的借官能团反应的研究，并取得超预期成果。我们已经通过论文发表的方式定义了借官能团反应中的借氰反应、借炔反应、借芳基反应以及借吡啶甲基反应等。我们在计划中的过渡金属催化借氰反应和借炔反应已经顺利的实施并取得了相应的结果。此外，我们还在其他的借官能团反应上也取得了不错的成绩，比如铑催化的吡啶导向的借芳基胺化反应以及碱催化的借吡啶甲基反应都取得了相应的结果。此类反应为含有官能团结构的醇类化合物提供了一个原子经济性高的转化方法。在项目的资助下，我们发表了5篇关于过渡金属催化的借官能团反应的SCI论文，主要包括有Chem. Sci., Chem. Commun., Org. Lett., Org. Chem. Front.以及Adv. Synth. Catal.等文章。