Han Gyuri, You Jihyun, Choi Junhyeon, Kang Eun Joo
Department of Applied Chemistry, Kyung Hee University, Yongin 17104, Korea.
Org Lett. 2024 Mar 29;26(12):2414-2419. doi: 10.1021/acs.orglett.4c00565. Epub 2024 Mar 15.
We present an innovative photoinduced cyanoalkyl radical addition methodology using -iminopyridinium reagents derived from cyclic ketones. Mechanistic investigations reveal the association of the excited Hantzsch ester and iminopyridinium with pyridyl radical generation. The ensuing cascade involving homolytic N-N bond and C-C bond cleavage of the pyridyl radical ultimately leads to the formation of cyanoalkyl radical species, leading to diverse Giese-type products. The method showcases versatility and synthetic utility in late-stage functionalization.
我们展示了一种创新的光诱导氰基烷基自由基加成方法，该方法使用源自环状酮的-亚氨基吡啶鎓试剂。机理研究揭示了激发态的汉斯酯和亚氨基吡啶鎓与吡啶基自由基生成之间的关联。随后涉及吡啶基自由基的均裂N-N键和C-C键断裂的级联反应最终导致氰基烷基自由基物种的形成，从而产生多种吉斯型产物。该方法在后期官能团化中展现出多功能性和合成实用性。
