芳基高碘试剂参与的氮杂螺烯的设计、合成与性质研究

螺烯是一类邻位稠合非平面的化合物，独特的结构使其在材料、医药、金属有机和催化等诸多领域应用广泛。而将氮原子引入到螺烯分子中，就得到结构、电性和功能新颖的氮杂螺烯分子，这类研究引起了化学家们的极大兴趣。然而，螺环结构特殊，传统上多以复杂多官能团的前体分子经加成、缩合、取代或环加成反应来构建，步骤多、效率低，难以对氮原子位置和螺环手性进行调控，这使得氮杂螺烯分子制备困难，研究也不充分。因此，发展新颖高效、高选择性的氮杂螺烯构建方法具有重要的科学意义。.本项目希望发展合成氮杂螺烯的新策略：设计底物芳基高碘试剂与腈、烯或炔烃等为原料一步合成氮杂螺烯，原料易得、反应便捷、选择性可控，容易大规模制备，可拓展到多元杂环螺烯体系。进一步会研究利用含手性辅基底物或者催化剂实现氮杂螺烯的不对称合成。最后，对于合成的螺烯可进行性质、配位、衍生化和催化性能研究，拓展氮杂螺烯的应用范围。

Helicenes have been received much attention with academic curiosity because they show non-planar ortho-fused characteristics and exhibit the feature of helical chirality. And they are privileged scaffolds widely used in many fields. The substitution of helicenes with nitrogen atom could produce aza-helicenes with unique structure, electron properties and functionality. Due to the special helix structure, the skeletons are normally constructed by addition, condensation, substitution or cycloaddition reactions with poly-functionalized precursors, which make the synthesis less efficiency and less selectivity on the chirality and position of N-atom. Hence, the development of novel efficient and selective methods to prepare aza-helicenes are highly important.. This program is focused on the design and synthesis of novel aza-helicene molecules. Based on the rational design, diaryliodonium salts, nitriles and alkenes or alkynes are subjected to react in one-step to synthesize aza-helicenes. And this strategy is readily extended to large-scale and prepare poly-aza or polycyclic helicenes. Moreover, the chiral helicenes are designed to synthesize with chiral auxillary groups or catalysts. Finally, the properties, coordination chemistry, deviation and catalytic properties will be investigated.