低价铁、钴、镍金属氢化物催化不饱和烃的选择性官能团化反应研究

Unsaturated hydrocarbons are important bulk products of petroleum and coal chemical industry, the crucial foundation of national economy, and essential natural resources for the sustainable development of our country. Hydrofunctionalization of unsaturated hydrocarbons provides a straightforward and efficient route for their transformation by introducing the desired functional groups directly. On the other hand, non-precious transition metals (such as iron, cobalt and nickel) have attracted a lot of attention owing to their high natural abundance, bio-compatibility and unique catalysis. This project focuses on the using of low-valent iron, cobalt, nickel-metal hydride generated in situ as catalyst, which undergoes facile insertion step into unsaturated hydrocarbons to form alkyl- or alkenyl-metal intermediate. The intermediacy of such species enables reactions with functional groups to achieve selective functionalization of unsaturated hydrocarbons, including arylation, alkylation, amination, etc. in mild conditions, high effiency and good selectivity. It is hoped that through the implementation of this project, practical methods for catalyst activation will be well developed, new catalytic system will be established to provide a new path for the discovery of new selectivity or new reaction for functionalization of unsaturated hydrocarbons, which also expand the application range of the first transition metal catalysis.

不饱和烃化合物是石油化工以及煤化工中的重要产品，是国民经济的重要物质基础和我国可持续发展不可或缺的物质资源。不饱和烃的氢官能团化可以直接引入所需要的官能团，实现不饱和烃的物质转化，方法简洁高效。另一方面，铁、钴、镍等廉价过渡金属具有储量丰富、生物兼容性好、催化活性独特的特点，受到越来越多的关注。本项目着重于开展将原位产生的低价铁、钴、镍金属氢化物作为催化剂，实现烯烃、炔烃、联烯等不饱和烃的选择性官能团化，包括氢芳基化、氢烷基化、氢胺化等反应。该类反应利用不饱和烃与金属氢键的插入后形成的烷基、烯基金属中间体，与过渡金属偶联相结合，具有条件温和、催化效率高、选择性控制好等优点。希望通过本项目的实施，发展实用的铁、钴、镍催化剂的活化方法，建立新的催化体系，为不饱和烃官能团化新反应新选择性的发现提供新路径，同时进一步拓展第一过渡金属催化的应用范围。

从价廉易得的烯烃出发，通过烯烃的官能团化反应可以直接引入所需要的官能团，具有出色的原子经济性和步骤经济性。本项目利用导向基团策略，实现了镍催化非活化烯烃的迁移氢烷基反应和氢芳基化反应，反应具有优异的区域选择性。我们也将该策略拓展到烯烃双官能团化反应中，包括双碳官能团化、芳基胺化、芳基硫醚化、芳基硼化等碳杂原子双官能团化和远程双官能团化反应。该类反应通过转金属化、迁移插入后形成的镍-烷基中间体，与偶联化学相结合，建立了多种新型反应体系，且具有条件温和、催化效率高、选择性控制好等优点。项目的研究建立了系列简洁高效、可持续的烯烃官能化新方法，可望为精准构筑合成结构多样性的复杂化合物和建立新化合物库提供新的途径和思路。