Synthesis of New Chiral Bidentate Isonitrile–Acyclic Diaminocarbene Palladium(II) Compounds and Their Catalytic Activity

Five new chiral bidentate isonitrile–diaminocarbene palladium­(II) complexes (<b>5a</b>–<b>5e</b>) as well as the bis-diaminocarbene complex <b>6</b> were prepared by metal-mediated nucleophilic addition of amines to the corresponding bisisonitrile–palladium­(II) compound <b>4</b>. The new chelates were fully characterized by 1D and 2D NMR experiments, IR, and ESI-MS. In addition, the X-ray structure of <b>5a</b>, <b>5c</b>, and <b>6</b> could be analyzed, showing different sterical properties. We furthermore investigated the relationship between their structure and their catalytic activity. The mixed ligand complexes <b>5a</b> and <b>5c</b> showed high activity both in Suzuki–Miyaura cross-coupling and in intermolecular asymmetric allylic alkylation (AAA) reactions as well as moderate chiral induction in the AAA.