Highly nucleophilic dipropanolamine chelated boron reagents for aryl-transmetallation to iron complexes
Highly nucleophilic dipropanolamine chelated boron reagents for aryl-transmetallation to iron complexes
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DOI：
10.1039/c5dt03835a
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Ingleson, Michael J.
中科院分区：
文献类型：
--
作者：
Dunsford, Jay J.;Clark, Ewan R.;Ingleson, Michael J.
以硼酸为原料直接合成了二丙醇胺螯合的芳基和杂芳基硼酸酯。相应的阴离子硼酸盐易于通过去质子化获得，并且与其他常见硼酸盐相比，表现出烃基亲核性的增加。新的硼酸盐证明胜任镁或锌添加剂的自由，直接硼到铁的烃基transmetallations与明确定义的铁（II）（前）催化剂。新硼酸盐试剂在代表性Csp（2）-Csp（3）交叉偶联中的应用导致几乎唯一的均偶联，除非偶联在锌添加剂存在下进行。
New aryl-and heteroarylboronate esters chelated by dipropanolamine are synthesised directly from boronic acids. The corresponding anionic borates are readily accessible by deprotonation and demonstrate an increase in hydrocarbyl nucleophilicity in comparison to other common borates. The new borates proved competent for magnesium or zinc additive-free, direct boron-to-iron hydrocarbyl transmetallations with well-defined iron(II) (pre)catalysts. The application of the new borate reagents in representative Csp(2)-Csp(3) cross-coupling led to almost exclusive homocoupling unless coupling is performed in the presence of a zinc additive.