Graduate School of Biomedical and Health Sciences, Hiroshima University.
Chem Pharm Bull (Tokyo). 2024;72(10):890-893. doi: 10.1248/cpb.c24-00431.
We studied the reaction pathway of our reductive Heck hydroarylation using a palladium catalyst and a hydrosilane. A key question to verify the reaction mechanism was which active species, Ar-Pd-I or Si-Pd-H, first performs migratory insertion into the alkenes. Identifying this step is crucial to elucidate the reaction mechanism. To address this, we designed a substrate containing two trisubstituted alkenes and tested its product. The results suggest that the migratory insertion of Ar-Pd-I into the alkene is the initial step of the reaction. Furthermore, this reaction can construct a quaternary carbon center and give high yields with high functional group tolerance.
我们研究了钯催化剂和硅烷在还原 Heck 氢芳基化反应中的反应途径。验证反应机理的一个关键问题是，哪种活性物种，Ar-Pd-I 还是 Si-Pd-H，首先进行迁移插入到烯烃中。确定这一步骤对于阐明反应机理至关重要。为了解决这个问题，我们设计了一种含有两个三取代烯烃的底物并测试了其产物。结果表明，Ar-Pd-I 向烯烃的迁移插入是反应的初始步骤。此外，该反应可以构建季碳原子中心，并具有高产率和高官能团容忍度。
