氮杂环卡宾和过渡金属联合催化反应研究

This project will investigate the cooperative, cascade and sequential catalysis of N-heterocyclic carbene (NHC) and transition metal catalysts in organic reactions. The first part focuses on the NHCs/metals cooperative catalysis of the reactions of aldehydes and alpha, beta-unsaturated aldehydes with unactivated alkenes and propargylic esters. The study aims to develop the cooperative catalytic systems achieving the umpolung of both reactants at one step, and therefore accomplishing the reactions of aldehydes and unsaturated aldehydes with the unactivated alkenes and alkyne substrates. The second part is to investigate the cascade and sequential catalysis using a combination of N-heterocyclic carbene and transition metal catalysts. The reactions of ortho-alkynyl aromatic aldehydes and ortho-alkynyl substituted alpha, beta-unsaturated aldehydes with ortho-alkynyl alpha, beta-unsaturated ketones, the reactions of o-alkynyl- and o-alkenyl aromatic aldehydes with imines, the reactions between alpha, beta-unsaturated aldehydes and unsaturated imines, the reactions of aromatic aldehydes and enals with 1,3-dicarbonyl hydrazones will be systematic studied. The discovery of novel NHC/metal cooperative, cascade and sequential catalyzed reactions will lead to new strategies for the enantioselective syntheses of multifunctional carbocyclic, heterocyclic and sophisticated fused heterocyclic compounds.

本项目拟研究氮杂环卡宾和过渡金属协同、串联或序列催化的新型有机反应。研究内容分两部分：第一部分系探索氮杂环卡宾和过渡金属协同催化醛、alpha,beta-不饱和醛与非活化烯烃或炔丙基酯类化合物的反应；旨在建立一步完成两个反应底物极性反转的催化体系，实现醛、不饱和醛与非活化烯烃或炔烃底物的反应。第二部分是研究氮杂环卡宾与过度金属串联或序列催化的新反应，包括邻炔基芳醛、邻炔基不饱和醛与邻炔基不饱和酮的反应，邻炔基和烯基芳醛与亚胺的反应，不饱和醛与不饱和亚胺的反应，芳醛和不饱和醛与1，3-二羰基腙的反应等。通过开拓氮杂环卡宾与过度金属协同、串联或序列催化的新反应，建立不对称合成多功能化碳环和杂环化合物、以及构建新型复杂稠杂环体系的新策略。

本项目系研究氮杂环卡宾和过渡金属串联及序列催化新型有机反应，项目完成的工作有以下几个方面：.1. 研究了氮杂环卡宾和钯催化剂串联催化3-（o-甲酰苯酚基）丙烯酸酯与烯丙基酯的反应，发展了合成2,2-二取代苯并呋喃-3-酮衍生物的新方法。.2. 探索了氮杂环卡宾和二价铜盐或碱序列催化邻炔基苯甲醛与N-酰基亚胺的反应，实现了催化剂调控从相同底物选择性合成多官能团化茚酮和异苯并呋喃衍生物。.3.研究了氮杂环卡宾和手性钯催化邻硝基乙烯芳基烯丙醇酯与偶氮二酸酯的串联反应，发展了高效和对映选择性合成手性1H-2,3-苯并二氮杂卓类化合物的新方法。.4. 研究了一价银盐和手性三唑卡宾序列催化N'-(o-芳乙炔基亚苄基)磺酰肼与环丙基甲醛的不对称串联反应，建立了高效合成光学纯亚胺桥联苯并[c]氮杂䓬-3-酮类化合物的新方法。.5. 探索了一价银盐和手性三唑卡宾序列催化N'-(2-芳乙炔基-3-吡啶亚甲基)磺酰肼与邻芳酰乙烯基肉桂醛的不对称串联反应，实现了催化剂体系调控的选择性构造和立体异构体多样性合成。.6、发展了一种通过氮杂环卡宾催化的氮杂苯偶铟反应和自由基分子内串联环化反应合成新型桥连苯并[f][1,3]氧氮芳辛-6-酮的方法。