Chelation-Assisted Rhodium-Catalyzed Direct Amidation with Amidobenziodoxolones: C(sp2)–H, C(sp3)–H, and Late-Stage Functionalizations

Xu-Hong Hu??, Xiao-Fei Yang?, and Teck-Peng Loh*?

? Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China

? Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore

Abstract:Air-stable and convenient amidobenziodoxolones as an amidating reagent were disclosed to enable direct amidation on a wide range of C(sp²)–H bonds of (hetero)arenes and alkenes, as well as unactivated C(sp³)–H bonds under Rh^IIIcatalysis. The approach to access 49 examples of structurally diverse amides is featured by mild conditions, complete chemoselectivity and regioselectivity, broad substrate scope (not limited to strongly heterocyclic coordinating groups), and tolerance of valuable functional substituents, such as unprotected amine and hydroxyl groups. The synthetic applicability of this protocol is also demonstrated by late-stage functionalization of biologically important scaffolds.

ACS Catalysis2016,6, 5930–5934 (2016年影响因子: 9.3).