酰胺官能化的烯、炔烃环化反应研究

Cyclization of alkenes or alkynes containing amide moiety represents an important strategy to construct heterocycles. In our previous works, highly efficient cyclizations of propargylamides for selective synthesis of oxazoles and their derivatives were developed. Substrate-controlled oxygen transfer reactions of propargylamides proceeded well in the presence of NIS and TMSN3, providing the corresponding imidazoles and tetrazoles with high regioselectivity. Allenylamides, generated by the isomerization of propargylamides, could undergo Pd-catalyzed cyclization to give 3-Ts substituted pyrroles. Thus, cyclization of alkenes or alkynes containing amide moiety such as propargylamides and allenylamides will be studied in details in the research proposal. The possible outcomes might allow us find new reaction patterns and catalytic systems to prepare structurally complex heterocycles. To gain a better understanding of the essence of the cyclizations, additional efforts will be made to elucidate the mechanisms. The successful implementation of this project will make a significant contribution to the field of heterocycle synthesis as well as the discovery of catalytic systems and new reaction patterns for the synthesis of heterocycles.

酰胺官能化的烯、炔烃环化反应是合成杂环化合物的重要方法。在前期的工作中，我们发现可以通过炔丙酰胺的环化反应来高选择性地合成一系列噁唑及其衍生物。在NIS/TMSN3中，炔丙酰胺可以发生底物控制的氧原子转移反应，选择性地合成咪唑和四唑。而它的异构化产物联烯酰胺则可发生Pd催化的环化反应生成3-Ts取代吡咯化合物。由此本项目将详细研究炔丙酰胺和联烯酰胺等酰胺官能化的烯、炔烃的环化反应，发现新的反应条件和催化体系来合成结构多样的杂环，研究反应机理，揭示其本质。从而对杂环合成化学、环化反应新催化体系和新反应的发现作出贡献。

酰胺官能化的烯、炔烃环化反应是合成杂环化合物的重要方法。在自然科学基金面上项目（21572225）的资助下，本项目详细研究了炔丙酰胺、炔酰胺、酰胺官能化二炔及烯炔的环化反应，发展了多种过渡金属和酸催化体系，高选择性地构建咪唑、四唑、噁唑、喹啉等杂环化合物。在该基金资助下，培养了4名博士研究生，发表了7篇研究论文，申请了8项专利。