路易斯碱调控、可见光催化高效构建有机硼化物及其应用研究

可见光氧化还原催化具有独特的反应性及条件温和的特点，如何利用可见光催化实现具有多功能有机硼化物的合成是有机化工研究中非常重要的前沿领域。现有的硼源存在易水解、稳定性差、制备过程复杂等不足，严重阻碍了可见光催化硼化技术的发展。本项目利用经济、易得、稳定的吡啶类路易斯碱硼烷加合物作为可见光催化硼源，设计合成系列新型吡啶及含氮杂环类路易斯碱硼烷加合物，通过系统结构调整实现大范围调控其可见光催化特性，大幅拓展反应性匹配的反应原料范围；设计在路易斯碱骨架上引入各类联接片段，通过将反应物“锚定”在路易斯碱上的策略，实现高效区域和立体选择性硼化；通过共聚或点击化学将路易斯碱固载于高分子材料上，开发高效“一锅法”连续反应硼化技术及其基于可见光催化的连续反应绿色化工过程。项目的完成将丰富可见光催化的设计策略和有机硼化物的合成途径，为含硼精细化学品的绿色合成提供新的解决方案。

Visible-light photoredox catalysis features characteristic reactivities and mild reaction conditions. How to prepare versatile organoboron compounds through visible-light photocatalysis is the edge-cutting frontier in organic chemical engineering. The issues for the current boron sources，including susceptibility for hydrolysis, instability, and complexity for preparation, which would severely stumble the advances of visible-light photocatalytic borylation. In this proposal, pyridine-based Lewis base borane adducts serve as inexpensive, readily available, stable boron sources in the visible-light photocatalysis. A series of novel Lewis base borane adducts derived from pyridine as well as other heterocycles are to be designed and prepared, whose photocatalytic capability would be systematically studied by modulating their structures to significantly expand their reaction scope via their matchup reactivities. The challenging regioselective and stereoselective borylation would be achieved by anchoring starting material onto adducts, where a linker is preinstalled to the Lewis base skeleton. The Lewis base can be immobilized on polymers through copolymerization or click chemistry to exploit efficient “one-pot” continuous borylation technique and continuous green process of chemical engineering. The completion of this proposal would enrich the design strategy of visible-light photocatalysis and synthetic routes for organoboron compounds and offer new solution and strategy for the green preparation of boron-containing fine chemicals.