三取代苯乙烯的氢胺化反应
首发时间:2018-01-31
摘要:为了实现三取代苯乙烯在区域选择性氢胺化反应,我们在这里报道可见光催化的方法,以氟代磺酰胺酯为氮源,以廉价染料番红O为光催化剂。季碳胺的产率从中等到良好。同时我们还实现了便捷的磺酰酯基团的脱除,给出了含苄基的alpha-季碳胺。经过密度泛函理论计算,我们发现对三取代苯乙烯的单电子氧化,会在烯烃的高苄位聚集正电荷密度,进而引发C-N键的生成,在此基础上我们提出了一个硫自由基和薯红T协同催化的光氧化还原催化氢胺化反应机理。
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Hydroamination reaction of trisubstituted styrenes
Abstract:To achieve regioselective hydroamination of trisubstituted styrenes, a visible light catalytic protocol employing sulfamate as nitrogen source was reported with safranine O as photocatalyst. The ?alpha-tertiary amine derivative was achieved with with moderate to good yield. The alpha-tertiary sulfamate could be deprotected conveniently, giving free alpha-tertiary amine in high yield. With DFT computational study, we found the positive charge in the cationic radical from a single electron oxidation of trisubstituted styrene focused on the homobenzylic position. This charge distribution leads to the formation of C-N bond. We proposed a safranin O/thiyl radical synergistic catalysis in the photoredox hydroamination reaction.
Keywords: visible light photoredox alkene hydroaminatioin safranin O
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