本部分工作从研究烯丙基硅烷的氧化反应出发,对α硅基烯丙基自由基的反应性和区域选择性进行了一些探讨,并用这种氧化反应及其产物的一些反应合成了几个天然产物。 在研究烯丙位氧化反应过程中,我们发现在Cu~+催化过氧叔丁醇可将许多烯丙基硅烷氧化成相应的β-硅基α,β不饱和酮。在同类反应中,这个系统被证明是迄今为止氧化能力最强的。从反应所体现的区域选择性可见,硅基可以活化α-C-H键并稳定所生成的α自由基。用烯基硅烷进行同样的反应,由于硅基的活化作用失去,反应性和选择性都大 This part of the work from the allylic silane oxidation reaction, the α-silyl allyl reactivity and regional selectivity of some of the discussion and use of this oxidation reaction and the reaction of some of its products synthesized a few Natural product. In the study of the allylic oxidation reaction, we found that many allyl silanes can be oxidized to the corresponding β-silyl α, β unsaturated ketones in Cu ~ + -catalyzed t-butyl alcohol. In a similar reaction, this system proved to be the strongest oxidized so far. It can be seen from the regioselectivity reflected by the reaction that silicon groups can activate α-C-H bonds and stabilize the α-radicals generated. The same reaction with alkenylsilanes results in loss of reactivity and selectivity due to the loss of activation of the silicon group