Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA.
Angew Chem Int Ed Engl. 2017 Aug 7;56(33):9833-9836. doi: 10.1002/anie.201704948. Epub 2017 Jul 13.
Heterobiaryls are important pharmacophores that are challenging to prepare by traditional cross-coupling methods. An alternative approach is presented where pyridines and diazines are converted into heteroaryl phosphonium salts and coupled with aryl boronic acids. Nickel catalysts are unique for selective heteroaryl transfer, and the reaction has a broad substrate scope that includes complex pharmaceuticals. Phosphonium ions also display orthogonal reactivity in cross-couplings compared to halides, enabling chemoselective palladium- and nickel-catalyzed coupling sequences.
杂芳基是一类重要的药效团，但通过传统的交叉偶联方法来制备具有挑战性。本文提出了一种替代方法，即将吡啶和哒嗪转化为杂芳基鏻盐，并与芳基硼酸偶联。镍催化剂对选择性杂芳基转移具有独特的作用，该反应具有广泛的底物范围，包括复杂的药物。与卤化物相比，鏻盐在交叉偶联中表现出正交反应性，从而能够实现钯和镍催化的偶联序列的化学选择性。
