Mechanistic Insight Leads to a Ligand Which Facilitates the Palladium-Catalyzed Formation of 2-(Hetero)Arylaminooxazoles and 4-(Hetero)Arylaminothiazoles.
Mechanistic Insight Leads to a Ligand Which Facilitates the Palladium-Catalyzed Formation of 2-(Hetero)Arylaminooxazoles and 4-(Hetero)Arylaminothiazoles.
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DOI：
10.1002/anie.201705525
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发表时间：
2017-08-21
期刊：
影响因子：
--
通讯作者：
Buchwald SL
中科院分区：
文献类型：
--
作者：
Olsen EPK;Arrechea PL;Buchwald SL
利用机理的洞察力，开发了一种新的配体（EPhos）用于pd催化的伯胺和芳基卤化物之间的C-N交叉偶联。在c3位置使用异丙氧基有利于配体负载的Pd（II）配合物的c键异构体，并显著提高了反应性。以二磷为基础，NaOPh为温和均相碱的催化剂体系在生成4-芳基氨基噻唑和高官能化2-芳基氨基磺唑方面是非常有效的。以前，使用pd催化的方法不容易获得这些。基于BrettPhos相关配体的结构活性关系，开发了一种新的用于pd催化C-N交叉偶联的配体EPhos。该配体成功地应用于pd催化形成2-（杂）芳基氨基ooxazoles和4-（杂）芳基氨基噻唑，这些结构以前被证明是难以通过过渡金属催化形成的。
Using mechanistic insight, a new ligand (EPhos) for the Pd-catalyzed C–N cross-coupling between primary amines and aryl halides has been developed. Employing an isopropoxy group at the C3-position favors the C-bound isomer of ligand-supported Pd(II) complexes and leads to significantly improved reactivity. The use of a catalyst system based on EPhos with NaOPh as a mild homogeneous base proved to be very effective in the formation of 4-arylaminothiazoles and highly functionalized 2-arylaminooxazoles. Previously, these were not readily accessible using Pd-catalyzed methodology. A new ligand, EPhos, for Pd-catalyzed C–N cross-couplings has been developed based on a structure activity relationship of BrettPhos related ligands. The ligand was succesfully applied in the Pd-catalyzed formation of 2-(hetero)arylaminooxazoles and 4-(hetero)arylaminothiazoles, structures that have previously proven problematic to form by transition metal catalysis.
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