Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
X-ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.
Angew Chem Int Ed Engl. 2019 May 6;58(19):6391-6395. doi: 10.1002/anie.201900095. Epub 2019 Apr 1.
Base-metal catalysts capable of enabling the assembly of heteroatom-dense molecules by cross-coupling of primary heteroarylamines and (hetero)aryl chlorides, while sought-after given the ubiquity of unsymmetrical di(hetero)arylamino fragments in pharmacophores, are unknown. Herein, we disclose the new "double cage" bisphosphine PAd2-DalPhos (L2). The derived air-stable Ni pre-catalyst C2 functions well at low loadings in challenging test C-N cross-couplings with established substrates, and facilitates the first Ni-catalyzed C-N cross-couplings of primary five- or six-membered ring heteroarylamines and activated (hetero)aryl chlorides, with synthetically useful scope that is competitive with Pd catalysis.
能够通过仲芳基胺和（杂）芳基氯的交叉偶联来实现杂原子密集分子组装的基底金属催化剂，由于在药效团中普遍存在不对称双（杂）芳基二胺片段而备受关注，但目前尚不清楚。在此，我们公开了新的“双笼”双膦 PAd2-DalPhos（L2）。衍生的空气稳定的 Ni 前催化剂 C2 在具有挑战性的测试 C-N 交叉偶联中，在低负载下表现良好，并且能够实现第一个 Ni 催化的仲芳基胺和活性（杂）芳基氯的 C-N 交叉偶联，具有与 Pd 催化相当的具有合成有用范围的竞争力。
