可见光促进钴催化烯烃杂（芳）化烷基化反应研究

The difunctionalization of alkene is one of the most important reactions in the synthetic organic chemistry. So far, a series of alkene difunctionalization reactions, such as hetero-difunctionalization (oxyamination eg.) and aryl-difunctionalization (arylamination eg.) reactions, have been well developed. However, the alkyl-difunctionalization reaction of alkene, especially those from unactivated alkyl halide, is still waiting to be studied. Our proposal will focus on the development of dual photoredox and cobalt catalytic system for the hetero- and aryl-alkylation reactions of alkenes by using unactivated alkyl halides. Several intramolecular cyclization/alkylation reactions, such as oxyalkylation, aminoalkylation and arylalkylation, of alkenes are proposed to be developed. The scope of unactivated alkyl halides will be fully investigated. The regioselective intramolecular cyclization/alkylation reactions of conjugated dienes are also proposed to be developed. Finally, the intermolecular reactions of alkenes, unactivated alkyl halides and nucleophiles will be studied. We anticipate that the development of these methods will be useful complement of the present methods for the difunctionalization of alkene, which will make the difunctionalization reactions more attractive.

烯烃双官能团化反应是有机合成化学研究中最为重要的反应之一。目前，包括羟胺化、芳胺化在内的烯烃杂化双官能团化和芳化双官能团化反应都已得到了系统而深入的研究。相比之下，烯烃的烷基化双官能团化反应研究进展缓慢。其中，非活性卤代烃参与的烯烃双官能团化反应仍然有待于突破。我们将采用光催化和钴催化组成的双重催化体系，发展在特定条件下烯烃、非活性卤代烃和亲核试剂的杂（芳）化烷基化反应。拟发展分子内烯烃与非活性卤代烃的氧化烷基化、胺化烷基化和芳化烷基化反应，挖掘卤代烷烃在烯烃双官能团化反应中的应用潜力；拟发展共轭二烯的分子内杂化烷基化和芳化烷基化反应，实现区域选择性可控合成；拟发展烯烃、非活性卤代烃和亲核试剂的三分子加成反应。我们期望通过这一系列的研究来建立烯烃杂（芳）化烷基化反应的完整体系，进一步完善烯烃的双官能团化反应，提升该类反应在有机合成中的应用价值。

碳–碳键的构筑是有机合成化学领域的核心问题。过渡金属催化非活性烷基亲电试剂的活化与烷基化反应是实现Csp3–Csp3和Csp3–Csp2精准构筑的有效方法，也是有机合成方法学研究领域的热点和难点问题。本项目首先探索光和钴双催化体系下烯烃环化烷基化反应的可行性；在此基础上，发展了一类新的廉价金属催化体系，实现了一系列非活性烷基亲电试剂的活化和烷基化反应。首次实现了非活性烷基溴代物与烷基碳酸酯的烷基化反应，为Csp3–Csp3键的构筑提供了新的途径；实现了非活性烷基磺酸酯与烯基磺酸酯的烷基化反应，解决了烷基环烯多样性合成的难题；实现了首个烯丙醇与亲电试剂的烯丙基化反应，为Tsuji-Trost反应的研究开辟了新的方向。