报告题目：C-H Amidation via Metal Nitrenoid Transfer: Reaction Development and Validation of Nitrene Intermediates

报 告 人：Sukbok Chang （Korea Advanced Institute of Science & Technology）

邀 请 人：黄良斌教授

报告时间：2024年11月08日（星期五）下午14:30-15:30

报告地点：逸夫工程馆四楼会议室

主办单位：化学与化工学院&广东省功能分子工程重点实验室

报告人简介：

Sukbok Chang教授，韩国科学技术院化学系教授，有机化学家，ACS Catalysis副主编。1982年本科毕业于高丽大学，1996年博士毕业于哈佛大学，1996年至1998年在美国加州理工学院做博士后研究；1998年至2002年任韩国梨花女子大学助教授，2008年至2011年任韩国科学技术院化学系系主任，2012年至今任催化烃官能团化研究中心主任，2018年至今任韩国科学技术院特聘教授。

报告摘要：

Direct amidation of C–H bonds is a highly desirable reaction considering high utility of amidated products in total synthesis, medicinal chemistry and materials science. In this context, we have developed a novel methodology that employs tailor-made Ir-based catalysts in combination with dioxazolone substrates to access a short-lived metal nitrenoid intermediate, thereby eventually leading to a construction of lactams via an outer-sphere C–H insertion pathway. More recently, we have successfully introduced an iridium-based catalyst system for asymmetric C−H amidation that enables facile construction of chiral lactams starting from commodity chemicals. The nitrenoid intermediacy was extensively investigated using mechanistic experiments, photocrystallography, and computational studies. In Particular, we designed a chromophoric octahedral rhodium complex with a bidentate dioxazolone ligand, in which photoinduced metal-to-ligand charge transfer initiates catalytic C–H amidation. X-ray photocrystallographic analysis of the Rh-dioxazolone complex allowed structural elucidation of the targeted Rh-acylnitrenoid and provided firm evidence that the singlet nitrenoid species is primarily responsible for acylamino transfer reactions. We also monitored in crystallo reaction of a nucleophile with the in situ generated Rh-acylnitrenoid, providing a crystallographically traceable reaction system to capture mechanistic snapshots of nitrenoid transfer.

近期代表性论文：

1) Park, Y.; Kim, Y.; Chang, S. Chem. Rev., 2017, 117, 9247.

2) Hong, S. Y.; Hwang, Y.; Lee, M.; Chang, S. Acc. Chem. Res. 2021, 54, 2683.

3) Hong, S. Y.; Park, Y.; Hwang, Y.; Kim, Y. B.; Baik, M.-H.; Chang, S. Science 2018, 359, 1016.

4) Park, Y.; Chang, S. Nat. Catal. 2019, 2, 219.

5) Hong, S.; Kim, D.; Chang, S. Nat. Catal. 2021, 4, 79.

6) Lee, J.; Lee, H.; Jung, H.; Kim, D.; Park, J. Chang, S. J. Am. Chem. Soc. 2020, 142, 12324.

7) Choi, H.; Lyu, X.; Kim, D.; Seo, S.; Chang, S. J. Am. Chem. Soc. 2022, 144, 10064.

8) Jung, H.; Kweon, J.; Suh, J.-M.; Lim, M. H. Kim, D.; Chang, S. Science 2023, 381, 525.

9) Lyu, X.; Seo, C.; Jung, H.; Faber, T.; Kim, D.; Seo, S.; Chang, S. Nat. Catal. 2023, 6, 784.