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Hybrid Palladium Catalyst Assembled from Chiral Phosphoric Acid and Thioamide for Enantioselective β-C(sp3)−H Arylation |
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| Authors: | Hua-Jie Jiang Xiu-Mei Zhong Zi-Ye Liu Rui-Long Geng Yang-Yang Li Prof Dr Yun-Dong Wu Prof Dr Xinhao Zhang Prof Dr Liu-Zhu Gong |
| Institution: | 1. Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026 China
These authors contributed equally to this work.;2. Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055 China;3. Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026 China |
| Abstract: | A hybrid palladium catalyst assembled from a chiral phosphoric acid (CPA) and thioamide enables a highly efficient and enantioselective β-C(sp3)−H functionalization of thioamides (up to 99 % yield, 97 % ee). A kinetic resolution of unsymmetrical thioamides by intermolecular C(sp3)−H arylation can be achieved with high s-factors. Mechanistic investigations have revealed that stereocontrol is achieved by embedding the substrate in a robust chiral cavity defined by the bulky CPA and a neutral thioamide ligand. |
| Keywords: | C−H activation kinetic resolution ligand effects palladium synthetic methods |