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共轭硅杂环化合物在太阳能电池、有机发光材料、荧光探针等领域都得到了广泛的关注和研究.其传统合成方法中因为往往需要计量的锂试剂或格氏试剂,官能团耐受性受到了极大的限制.近年来,包括北京大学化学与分子工程学院席振峰教授在内的一些科学家开拓的碳-硅键活化反应代表了一种构建含硅化合物的新方向.在此策略指引下,清华大学药学系何伟课题组设计了如下图所示的铑催化的串联分子内胺化/硅-碳(sp~3)键活化反应来快速高效合成共轭硅杂环化合物.研究发现,添加剂对该串联反应中关键的碳-硅键活化的化学选择性有重要的影响:在质子源(正辛醇)的作用下会发生硅-碳(sp~3)键活化得到共轭硅杂环化合物2,而在π酸(3,3-丙烯醛)存在时则发生硅-碳(sp~2)
Conjugated silicon heterocyclic compounds have attracted wide attention and research in the fields of solar cells, organic luminescent materials, fluorescent probes, etc. In the traditional synthesis methods, due to the often required measurement of lithium reagent or Grignard reagent, the functional group resistance is affected A great limit.In recent years, some scientists including Professor Xianfeng Zhen, Peking University School of Chemistry and Molecular Engineering, pioneered the carbon-silicon activation reaction represents a new direction for the construction of silicon-containing compounds.Under this strategy, He Wei, Department of Pharmacy, Tsinghua University, designed the rhodium catalyzed in-line molecular amination / silicon-carbon (sp ~ 3) bond activation reaction to rapidly and efficiently synthesize conjugated silicon heterocycles.It was found that the additives It has an important effect on the chemical selectivity of the key carbon-silicon bond activation in the tandem reaction: the activation of the silicon-carbon (sp ~ 3) bond by the proton source (n-octanol) Compound 2, whereas silicon-carbon (sp ~ 2) occurs in the presence of octanoic acid (3,3-acrolein)