亲电试剂与烯丙醇的烯丙基化反应

The transition-metal-catalyzed allylation reaction (Tsuji-Trost Reaction) is an attractive method for C-C bond formation. Among which, the direct allylation with allylic alcohol is more promising in terms of green chemistry. However, the reaction is confined to particular substrate, which restricts the development and application of this reaction. Generally, only the specific position of typical nucleophiles could be allylated. Although the use of organometallic reagents enables the allylation at a common aromatic ring, these reagents suffer from challenges such as low stability, low functional group compatibility and limited availability. We considered that the development of allylation reactions of electrophiles will fully overcome the present limitations. Our proposal will focus on the use of reductive cross-coupling strategy to achieve the allylation reactions of reactive electrophiles (Ar-Br、Alkenyl-OTf and Alkyl-Br etc.) with allylic alcohols. Then, the allylation reactions of unreactive electrophiles (Ar-OPiv, ArCH2-OMe and Alkenyl-OMe etc.) with allylic alcohols will be studied. Finally, we will investigate the asymmetric allylation reactions of electrophiles. The study of this project will provide a new strategy and synthetic route for the allylation reactions.

过渡金属催化的烯丙基化反应(Tsuji-Trost反应)是构筑C-C键的重要方法。其中，烯丙醇参与的烯丙基化反应是其绿色化研究的重要方向。然而，底物的局限性制约了反应的进一步发展和应用。目前，大部分反应仍限于发生在特殊亲核试剂的特定位点上；虽然使用金属试剂能实现普通芳环的烯丙基化，但是金属试剂稳定性不好、官能团兼容性差和种类相对稀少等不足也影响了反应的有效应用。发展亲电试剂的烯丙基化反应将是解决上述问题的重要途径。本项目拟采用Ni催化还原偶联的方法，实现Ar-Br、Alkenyl-OTf、Alkyl-Br等活性亲电试剂与烯丙醇的烯丙基化反应；在此基础上，进一步实现Ar-OPiv, ArCH2-OMe、Alkenyl-OMe等非活性亲电试剂与烯丙醇的烯丙基化反应；最终实现亲电试剂的不对称烯丙基化反应。本项目的开展将为烯丙基化反应的研究提供新思路、新途径。

醇的脱羟基偶联反应是有机合成领域的挑战性难题，但具有重要的研究价值。本项目旨在研究烯丙醇与芳基、烯基、烷基等亲电试剂的还原偶联反应。在项目的支持下，我们取得了一系列的创新成果。我们实现了烯丙醇与溴代芳烃的还原芳基化反应，实现了烯丙醇与烯基磺酸酯的还原烯基化反应；发展了动态动力学偶联策略，实现了苄醇与芳基亲电试剂的还原芳基化反应、苄醇的脱羟基自偶联反应；首次揭示了镍对季铵盐的单电子活化，实现了苄基季铵盐与烯基乙酸酯的还原偶联反应，报道了通过C-N和C-O切断构筑C-C键的新构键模式；首次实现氯硅烷与碳亲电试剂的还原偶联反应等等。工作揭示了新的化学，解决了一系列合成难题，拓展了新的研究空间。