Rational Design of an Iron-Based Catalyst for Suzuki-Miyaura Cross-Couplings Involving Heteroaromatic Boronic Esters and Tertiary Alkyl Electrophiles
Rational Design of an Iron-Based Catalyst for Suzuki-Miyaura Cross-Couplings Involving Heteroaromatic Boronic Esters and Tertiary Alkyl Electrophiles
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DOI：
10.1002/anie.201914315
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发表时间：
2020-02-25
影响因子：
16.6
通讯作者：
Byers, Jeffery A.
中科院分区：
文献类型：
--
作者：
Crockett, Michael P.;Wong, Alexander S.;Byers, Jeffery A.
介绍了一种合理设计的β-双烯酮亚胺配体负载的铁基催化剂，用于各种卤代烷与未活化的芳基硼酸酯之间的Suzuki-Miyaura交叉偶联反应。高催化剂活性导致广泛的底物范围，包括叔烷基卤化物和杂芳族硼酸酯。机理实验表明，铁基催化剂受益于β-二酮亚胺配体支持低配位和高度还原的铁酰胺中间体的倾向，这对于实现Suzuki-Miyaura交叉偶联反应所需的金属转移步骤非常有效。
Suzuki-Miyaura cross-coupling reactions between a variety of alkyl halides and unactivated aryl boronic esters using a rationally designed iron-based catalyst supported by beta-diketiminate ligands are described. High catalyst activity resulted in a broad substrate scope that included tertiary alkyl halides and heteroaromatic boronic esters. Mechanistic experiments revealed that the iron-based catalyst benefited from the propensity for beta-diketiminate ligands to support low-coordinate and highly reducing iron amide intermediates, which are very efficient for effecting the transmetalation step required for the Suzuki-Miyaura cross-coupling reaction.