College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China.
Org Lett. 2022 Jul 22;24(28):5090-5094. doi: 10.1021/acs.orglett.2c01867. Epub 2022 Jul 13.
We herein report an unprecedented pathway to access γ-lactams using acetonitrile analogues as coupling partners without oxidants, ligands, and Lewis acids. The reaction undergoes Rh-catalyzed C(sp)-H addition to carbon-bound nitriles with the aid of an amide traceless auxiliary followed by an annulation sequence, featuring a broad substrate scope, good functional group tolerance, and excellent chemo/stereoselectivity. Scale-up reactions and late-stage derivatizations highlight the potential synthetic utility of this methodology. A plausible mechanism is proposed based on mechanistic investigations.
我们在此报告了一种前所未有的途径，使用乙腈类似物作为偶联试剂，在没有氧化剂、配体和路易斯酸的情况下，合成γ-内酰胺。该反应在酰胺无痕迹助剂的辅助下，经 Rh 催化的 C(sp)-H 加成到碳键上的腈，然后进行环化反应，具有广泛的底物范围、良好的官能团耐受性和优异的化学/立体选择性。放大反应和后期衍生化突出了该方法的潜在合成实用性。根据机理研究提出了一个合理的机理。
