Selective Arylation and Vinylation at the Position of Vinylarenes
Selective Arylation and Vinylation at the Position of Vinylarenes
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DOI：
10.1002/chem.201203646
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发表时间：
2013-03-01
影响因子：
4.3
通讯作者：
Zhou, Jianrong (Steve)
中科院分区：
文献类型：
--
作者：
Zou, Yinjun;Qin, Liena;Zhou, Jianrong (Steve)
在苯乙烯和乙烯基芳烃的分子间Heck反应中，芳基和乙烯基基团通常插入在该位置。然而，在该位置的选择性插入非常罕见。在此，我们提供了Heck反应的调色板中缺失的部分，其给出>20：1的选择性。我们成功的关键是一个新的二茂铁1，1-双膦（dnpf），携带1-萘基。我们的机理研究表明，高选择性部分归因于dnpf的空间位阻效应。dnpf的刚性和庞大的1-萘基在空间上不利于插入。
In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the position. However, selective insertion at the position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 selectivity. The key to our success is a new ferrocene 1,1-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor insertion.