Yang Yuan, Song Ren-Jie, Li Yang, Ouyang Xuan-Hui, Li Jin-Heng, He De-Liang
State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082, China. srj0731@
Chem Commun (Camb). 2018 Feb 11;54(12):1441-1444. doi: 10.1039/c7cc08964c. Epub 2018 Jan 12.
A copper-catalyzed oxidative radical strategy to avoid the use of the highly expensive noble metal/ligand catalytic systems is described, which allows selective activation of dual chemical bonds around the Si-atom center relying on the nature of alkylsilanes. While for tertiary silanes selective functionalization of Si-H/silyl C(sp)-H bonds in intermolecular oxidative annulation cascades with N-(2-(ethynyl)aryl)acrylamides toward silino[3,4-c]quinolin-5(3H)-ones, when using secondary silanes and HSi(TMS), dual Si-H bonds or Si-H/Si-Si bonds are selectively cleaved leading to 4H-silolo[3,4-c]quinolin-4-ones.
本文描述了一种铜催化的氧化自由基策略，该策略避免使用昂贵的贵金属/配体催化体系，它能够依靠烷基硅烷的性质选择性地活化硅原子中心周围的双化学键。对于叔硅烷，在与N-(2-(乙炔基)芳基)丙烯酰胺进行分子间氧化环化级联反应时，Si-H/硅基C(sp)-H键可选择性官能化生成硅并[3,4-c]喹啉-5(3H)-酮；而当使用仲硅烷和HSi(TMS)时，双Si-H键或Si-H/Si-Si键会被选择性裂解，生成4H-硅并[3,4-c]喹啉-4-酮。
