Reactivity of Boryl- and Silyl-Substituted Carbenoids toward Alkynes: Insertion and Cycloaddition Chemistry
Reactivity of Boryl- and Silyl-Substituted Carbenoids toward Alkynes: Insertion and Cycloaddition Chemistry
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DOI：
10.1021/om501252m
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发表时间：
2015-02
期刊：
影响因子：
2.8
通讯作者：
A. Protchenko;Matthew P. Blake;Andrew D. Schwarz;Cameron Jones;P. Mountford;S. Aldridge
中科院分区：
文献类型：
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作者：
A. Protchenko;Matthew P. Blake;Andrew D. Schwarz;Cameron Jones;P. Mountford;S. Aldridge
报道了苯基取代的炔烃与四环三烯反应的三种模式，发现反应途径不仅取决于第14族元素的性质，而且还取决于支持的配体集。具有SnB或Ge-B键的体系经历插入化学，形成添加了硼烷的(乙烯基)SnII和GeII物种。对于双(氨基)锡烯，苯乙炔起到质酸的作用，生成具有独特桥联结构的SnII乙炔。通过[2+1]环加成反应获得SiIV的可能性决定了更强还原SiIII体系的反应性。
Three modes of reactivity of phenyl-substituted alkynes toward acyclic tetrelenes are reported, with reaction pathways found to be dependent not only on the nature of the group 14 element but also on the supporting ligand set. Systems featuring Sn–B or Ge–B bonds undergo insertion chemistry, forming borane-appended (vinyl)SnII and GeII species. With a bis(amido)stannylene, phenylacetylene acts as a protic acid, generating a SnII acetylide with a unique bridged structure. Reactivity toward a more strongly reducing SiII system is dominated by the possibility of accessing SiIV via [2 + 1] cycloaddition chemistry.