General High-Valent Nickel Metallocycle Catalyst for the Perfluoroalkylation of Heteroarenes and Peptides
Shubham Deolka, Ramadoss Govindarajan, Tatiana Gridneva, Michael C. Roy, Serhii Vasylevskyi, Pavan K. Vardhanapu, Julia R. Khusnutdinova, Eugene Khaskin
Abstract
We describe a unified nickel platform for the perfluoroalkylation of heteroarenes and peptides. Catalysis proceeds at room temperature without using photosensitizers. The catalytic protocol is distinguished by its simplicity, and its wide scope demonstrates its potential in the late-stage functionalization of natural products. The unified platform allows for the cost-effective use of specialty Togni reagents, leading us to develop a CC coupling protocol between arenes via a C 2 F 4 bridge. Both experimental and computational studies support the formation of a Ni IV intermediate and a radical mechanism.